JP5250303B2 - Propylene resin composition - Google Patents

Description

  The present invention relates to a propylene-based resin composition having excellent impact resistance, and more specifically, a propylene-ethylene copolymer component produced by a multistage polymerization method using a Ziegler-Natta catalyst or a metallocene catalyst as a main component, A crystalline propylene polymer component produced by a multistage polymerization method and a crystalline propylene polymer component and a copolymer in which a part of the propylene-ethylene random copolymer component are chemically bonded to each other And a propylene-ethylene copolymer component comprising a propylene-ethylene random copolymer component as an impact modifier component. Further, in addition to the above components, the present invention further relates to a propylene resin composition containing an ethylene / α-olefin elastomer or a styrene elastomer, and an inorganic filler, wherein the impact resistance is remarkably improved. .

Propylene resin, which is heavily used as an industrial material, is extremely excellent in rigidity and heat resistance, but has relatively low impact resistance, which is important as a physical property, so a random copolymer of propylene and ethylene, or polypropylene As a composition obtained by blending with a copolymer thereof, a technique for improving impact resistance has been often used.
Among them, such a composition obtained by a series of polymerization steps was obtained by producing crystalline polypropylene in the first step and propylene-ethylene random copolymer in the second step. Typically, it is called a propylene-ethylene block copolymer.

Such a propylene-ethylene block copolymer is usually produced industrially using a Ziegler-Natta catalyst, but the Ziegler-Natta catalyst generally has various active sites (so-called multisite). ), The molecular weight distribution and the comonomer composition distribution of the propylene-ethylene copolymer part are known to be wide. Thus, the propylene-ethylene block copolymer produced using a Ziegler-Natta catalyst has a wide composition distribution, so the rigidity-impact resistance balance of the molded product is relatively good, and the molecular weight distribution. The moldability is also good because of the large width. As described above, the propylene-ethylene block copolymer produced using a Ziegler-Natta catalyst exhibits excellent performance in various physical property balances, and thus includes interior and exterior of automobiles and packaging materials. It has been used in many industrial fields.
However, from the viewpoint of recent resource problems, energy problems, etc., the demand for further thinning and weight reduction of materials is not limited, and impact resistance performance to propylene-ethylene block copolymers which are impact resistant materials. The expectation for improvement is getting stronger.

Until now, in order to improve the rigidity, heat resistance and impact resistance of such a propylene-ethylene block copolymer in a well-balanced manner, the copolymer component has a sufficient crystallinity while maintaining sufficient impact resistance. It is thought that it is necessary to control the compatibility of polypropylene and copolymer components within an appropriate range, and by adding a compatibilizer component of polypropylene component and copolymer part, a technique to increase these compatibility Has been known for a long time (see, for example, Patent Documents 1 and 2).
In such a method, recently, the intrinsic viscosity and MFR of each component are further specified, and a copolymer component having a relatively low ethylene content and a copolymer component having a relatively low ethylene content as a compatibilizing agent are combined with the crystalline polypropylene component. Copolymers composed of components and having excellent impact resistance at low temperatures are also disclosed (see, for example, Patent Documents 3 and 4).
In order to improve the balance of rigidity, heat resistance and impact resistance of the propylene-ethylene block copolymer produced by a metallocene catalyst (so-called single site catalyst) which has been increasingly used recently, Similar to the method using a Ziegler catalyst, a propylene resin composition comprising a compatibilizer component of a metallocene propylene-ethylene copolymer and having an excellent balance of rigidity, heat resistance and impact resistance is prepared in at least three stages. Attempts have been made to produce by polymerization (see Patent Document 5).

  Furthermore, the inventors of the present application have disclosed that a propylene-ethylene block produced by a metallocene catalyst comprising at least three components including a compatibilizing component with respect to a propylene-ethylene block copolymer produced by a Ziegler-Natta catalyst. A technique for improving rigidity and impact resistance by adding a copolymer as a modifier has been proposed (for example, Japanese Patent Application No. 2006-34573).

As described above, as a technique for improving the impact resistance of a propylene-ethylene block copolymer produced with a Ziegler-Natta catalyst, many are compatible with a crystalline propylene component and a propylene-ethylene random copolymer component. Many attentions are paid to improving the impact resistance by modifying the properties of the interface, but the interface is modified to improve the compatibility between the crystalline part and the amorphous part. Since this leads to a decrease in the rigidity, it is extremely difficult to improve the rigidity-impact resistance balance, and it can be said that there is still room for examination.
JP-A-57-67611 JP 61-152442 A JP 2003-327642 A JP 9-48831 A International Publication No. WO95 / 27741

  In view of the technical improvement flow of the propylene-based resin material in the prior art, development of a propylene-based resin material having a further improved balance of rigidity and impact resistance is strongly desired. In view of the above problems, an object is to provide a propylene-based resin composition in which the balance between rigidity and impact resistance is improved, and particularly, impact resistance is remarkably improved.

  In order to solve the above-mentioned problems, the present inventors have conducted extensive research, and as a result, in improving the impact resistance of a propylene-ethylene block copolymer produced with a Ziegler-Natta catalyst, a specific metallocene compound Crystalline propylene containing a copolymer in which a part of a propylene-ethylene random copolymer component and a crystalline propylene component continuously produced by a multistage polymerization method using a catalyst containing Surprisingly, the rigidity is almost the same by using a propylene-ethylene copolymer component composed of a polymer component and a propylene-ethylene random copolymer component as an impact resistance improver. As a result, it was found that the impact resistance was remarkably improved, and the present invention was completed.

That is, according to the first aspect of the present invention, from 0.1 to 30 wt% propylene - ethylene copolymer component (A) 70 to 99.9% of propylene - ethylene copolymer component (B) The propylene-ethylene copolymer component (A) is obtained by continuously multistage polymerization of a crystalline propylene polymer component and a propylene-ethylene random copolymer component, and the following (A1) to (A6) The propylene-ethylene copolymer component (B) is obtained by continuously multistage polymerization of a crystalline propylene polymer component and a propylene-ethylene random copolymer component, and the following (B1 ) To (B3), a propylene-based resin composition is provided.
(A1) The amount of the component (AC) mainly composed of crystalline polypropylene, which is fractionated and determined by the temperature-programmed crystalline fractionation method, is 10 to 98 weights with respect to the total amount of the propylene-ethylene copolymer (A). The amount of the component (AA) mainly consisting of a propylene-ethylene random copolymer is 2 to 90% by weight,
(A2) The melt flow rate (MFRA) at 230 ° C. and a load of 2.16 kg of the propylene-ethylene copolymer (A) is 10 g / 10 min. That's it,
(A3) The melting point in DSC of the propylene-ethylene copolymer (A) is 156.1 ° C. or higher,
(A4) The melt flow rate MFRA-1 of the crystalline polypropylene component polymerized in the first stage is 40 g / 10 min. That's it,
(A5) The ethylene content of the copolymer component (AA) fractionated by the temperature rising crystalline fractionation method is based on the total amount of propylene and ethylene monomer in the copolymer component (AA). 20 to 80% by weight,
(A6) The melt flow rate MFRA-2 of the copolymer component (A) polymerized in the second stage is obtained by the following formula 1 ′, and the weight average molecular weight M _w AA of the component (AA) The following formula 1 is satisfied.
log (MFRA-2) ≦ -3.9 × log (MwA-A) + 19.9 ··· ( Equation 1)
log (MFRA) = {weight% of component (AC)} / 100 × log (MFRA-1) + {weight% of component (AA)} / 100 × log (MFRA-2) ( Formula 1 ')
(B1) The amount of the component (BC) mainly composed of crystalline polypropylene, which is fractionated and quantified by the temperature rising crystalline fractionation method, is 50 to 95 weights with respect to the total amount of the propylene-ethylene copolymer (B). The amount of the component (BA) mainly composed of a propylene-ethylene random copolymer is 5 to 50% by weight,
(B2) The melting point in DSC of the propylene-ethylene copolymer (B) is 155 ° C. or higher,
(B3) The melt flow rate MFRB-2 in the second stage in polymerized copolymer component (B), determined by the following formula 2 ', and the weight average molecular weight of the component _{(B-A) M w B} -A The following formula 2 is satisfied.
log (MFRB-2)> - 3.9 × log (MwB-A) + 21.4 ··· ( Equation 2)
log (MFRB) = {weight% of component (BC)} / 100 × log (MFRB-1) + {weight% of component (BA)} / 100 × log (MFRB-2) (...) Formula 2 ′)
Here, MFRB is the MFR of the entire propylene-ethylene copolymer (B).

According to the second invention of the present invention, in the first invention, the parameter λmax indicating the strain hardening property obtained from the extensional viscosity measurement of the propylene-ethylene copolymer (A) is less than 2.0. A propylene-based resin composition is provided.
According to the third invention of the present invention, in the first or second invention, the propylene-ethylene copolymer (A) is a graft copolymer in which a crystalline polypropylene component is a branch part. The propylene-type resin composition characterized by including is provided.
According to the fourth invention of the present invention, in any one of the first to third inventions, the propylene-based resin composition contains 0 to 40% by weight of an ethylene / α-olefin elastomer or a styrene elastomer and inorganic. A propylene-based resin composition comprising 0 to 40% by weight of a filler is provided.
Furthermore, according to the fifth invention of the present invention, there is provided a molded product obtained by injection molding the propylene-based resin composition of any one of the first to fourth inventions.

The propylene-based resin composition of the present invention comprises a propylene-ethylene copolymer component (A) and a propylene-ethylene copolymer component (B), and the propylene-ethylene copolymer component (A) Since the part has a specific structure that includes a graft copolymer in which the crystalline polypropylene component is a branch part, and satisfies the relationship between a specific MFR and a weight average molecular weight, the impact resistance remains substantially the same. The effect is remarkably improved and the balance between rigidity and impact resistance is excellent.
In addition, because of their excellent characteristics, it is suitable for injection molding, sheet molding, extrusion foam molding, large blow molding, etc., especially for interior and exterior materials of vehicles such as automobiles and packaging packaging materials such as electrical products. Can do.

The propylene-based resin composition of the present invention comprises two types of propylene-ethylene copolymer components having specific properties, and the propylene-ethylene copolymer component (B) as the main component is in the total amount of the resin composition. On the other hand, 50.0 to 99.9% by weight, and the propylene-ethylene copolymer component (A) as a modifier is comprised of 0.1 to 50% by weight.
The preferred range is 1 to 40% by weight of component (A), 60 to 99% by weight of component (B), more preferably 5 to 30% by weight of component (A), and 70% of component (B). ~ 95 wt%. When the content of the component (A) is below this range, the impact resistance improving effect is not sufficient, and when it exceeds, the rigidity and heat resistance are inferior.
Hereinafter, each component will be described in detail.

1. Propylene-ethylene copolymer component (A)
The propylene-ethylene copolymer (A) according to the present invention is produced by a continuous multi-stage process, polymerizes crystalline polypropylene in the first stage, and propylene-ethylene random copolymer component in the second stage and thereafter. Is produced by the same steps as those conventionally called propylene-ethylene (block) copolymers obtained by polymerizing the above. In particular, it is a copolymer characterized by satisfying the relationship between a specific MFR and a weight average molecular weight because of its structural characteristics.

1-1. Crystalline polypropylene polymerized in the first stage In the present invention, the crystalline polypropylene polymerized in the first stage of the component (A) mainly refers to a propylene homopolymer, but propylene unless it departs from the spirit of the invention. And a small amount of a copolymer with other α-olefin having 2 to 20 carbon atoms. Here, examples of other α-olefins include ethylene, 1-butene, 1-hexene, 1-octene and the like. Crystalline polypropylene is a propylene homopolymer component because it is a component contributing to rigidity and heat resistance in the propylene-ethylene copolymer (A).
The MFR of this component is greatly related to the fluidity of the propylene-ethylene copolymer (A). Therefore, the MFR (MFR1) of the crystalline polypropylene polymerized in the first stage is 40 g / 10 min. That is necessary. Preferably 50 g / 10 min. That's it. If it is less than this, the fluidity is insufficient, and this is not particularly preferred for injection molding applications. It is well known to those skilled in the art that the MFR of the polypropylene resin satisfies a linear relationship when plotted on a logarithmic plot with the weight average molecular weight, and the MFR is 40 g / 10 min. The above is about 150,000 or less in weight average molecular weight.
In addition, MFR (MFR1) and weight average molecular weight of the crystalline polypropylene polymerized in the first stage can be evaluated by extracting a sample during polymerization.

1-2. Propylene-ethylene random copolymer polymerized in the second stage and thereafter In the second stage and later of the multistage polymerization method, the propylene-ethylene random copolymer component is mainly polymerized. Here, unless it deviates from the meaning of the present invention, a small amount of other α-olefins such as 1-butene, 1-hexene, 1-octene and the like may be copolymerized.
The ethylene content in the copolymer polymerized in the second stage and thereafter is 20 to 80% by weight with respect to the total of propylene and ethylene monomer in the copolymer. Preferably it is 25 to 75 weight%, More preferably, it is 30 to 70 weight%. Those having an ethylene content outside this range are inferior in impact resistance. A method for identifying the ethylene content in the copolymer will be described later.

1-3. Determination of the ratio between the crystalline polypropylene component and the copolymer component in the propylene-ethylene copolymer, the ethylene content in the copolymer, and the weight average molecular weight Mainly crystals in the propylene-ethylene copolymer (A) The ratio of the component (A-C) composed of a conductive polypropylene and the component (AA) composed mainly of a propylene-ethylene random copolymer, and the ethylene content and the weight average molecular weight in the copolymer are determined by the temperature rising solubility. It can obtain by analyzing with the apparatus which combined the fractionation apparatus, GPC, and FT-IR. Details of this method are described in Japanese Patent Application Laid-Open No. 2003-147035, but a specific procedure will be simply described below.

a. Analytical device to be used [Cross separation device]
Diamond Instruments CFC T-100 (abbreviated as CFC)
[Fourier transform infrared absorption spectrum analysis]
FT-IR Perkin Elmer 1760X
A fixed wavelength infrared spectrophotometer attached as a CFC detector is removed and an FT-IR is connected instead, and this FT-IR is used as a detector.
The transfer line from the outlet of the solution eluted from the CFC to the FT-IR is 1 m long, and the temperature is maintained at 140 ° C. throughout the measurement. The flow cell attached to the FT-IR has an optical path length of 1 mm and an optical path width of 5 mmφ, and the temperature is maintained at 140 ° C. throughout the measurement.
[Gel permeation chromatography (GPC)]
The GPC column at the latter stage of the CFC is used by connecting three AD806MS manufactured by Showa Denko in series.

b. CFC measurement conditions Solvent: Orthodichlorobenzene (ODCB)
Sample concentration: 4 mg / mL
Injection volume: 0.4mL
Crystallization: The temperature is lowered from 140 ° C. to 40 ° C. over about 40 minutes.
Fractionation method: Fractionation temperature at the time of temperature-raising elution fractionation is 40, 100, 140 ° C., and fractionation is performed in all three fractions. In addition, the elution ratio (unit:% by weight) of the component eluting at 40 ° C. or lower (fraction 1), the component eluting at 40 to 100 ° C. (fraction 2), and the component eluting at 100 to 140 ° C. (fraction 3), respectively It is defined as W ₄₀ , W ₁₀₀ , and W ₁₄₀ . W ₄₀ + W ₁₀₀ + W ₁₄₀ = 100. Moreover, each fractionated fraction is automatically transported to the FT-IR analyzer as it is.
Solvent flow rate during elution: 1 mL / min

c. Measurement conditions of FT-IR After elution of the sample solution starts from GPC at the latter stage of the CFC, FT-IR measurement is performed under the following conditions, and GPC-IR data is collected for each of the above-described fractions 1 to 3.
Detector: MCT Resolution: 8 cm ^-1
Measurement interval: 0.2 minutes (12 seconds)
Integration times per measurement: 15 times

d. Post-processing and analysis of measurement results The elution amount and molecular weight distribution of the components eluted at each temperature are determined using the absorbance at 2,945 cm ⁻¹ obtained by FT-IR as a chromatogram. The elution amount is normalized so that the total elution amount of each elution component is 100%. Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene.

Conversion to molecular weight uses a general-purpose calibration curve with reference to “Size Exclusion Chromatography” written by Sadao Mori (Kyoritsu Shuppan). The following numerical values are used for the viscosity equation ([η] = K × M ^α ) used at that time.
[When creating a calibration curve using standard polystyrene]
K = 1.38 × 10 ⁻⁴ α = 0.70
[When measuring sample of propylene-ethylene block copolymer]
K = 1.03 × 10 ⁻⁴ α = 0.78
The ethylene content distribution (distribution of ethylene content along the molecular weight axis) of each elution component was determined by using the ratio of the absorbance at 2,956 cm ^{−1 and} the absorbance at 2,927 cm ⁻¹ obtained by GPC-IR. Ethylene content (weight) using a calibration curve prepared in advance using ethylene-propylene-rubber (EPR) and a mixture thereof whose ethylene content is known by polypropylene, ¹³ C-NMR measurement, etc. %).

The content of component (AA) and the ethylene content can be determined by the following formula.
Component (AA) content (% by weight)
_{= W 40 × A 40 / B} 40 + W 100 × A 100 / B 100
Ethylene content (weight%) in component (AA)
= (W ₄₀ × A ₄₀ + W ₁₀₀ × A ₁₀₀ ) / [component (AA) content]
Here, A ₄₀ and A ₁₀₀ are average ethylene contents (unit: wt%) in each fraction corresponding to W ₄₀ and W ₁₀₀ , and B ₄₀ and B ₁₀₀ are copolymers contained in each fraction. It is ethylene content (unit: weight%) of a component. Here, the average ethylene content A ₄₀ , A ₁₀₀ of fractions 1-2 is the weight ratio for each data point and the ethylene content for each data point (2,956 cm) in the absorbance chromatogram of 2,945 cm ^{−1. -1 and} the absorbance of 2,927 cm ^-1 ).
The ethylene content corresponding to the peak position in the differential molecular weight distribution curve of fraction 1 is defined as B ₄₀ (unit is% by weight). Further, it is defined as B ₁₀₀ = 100. Since the component (AA) is basically mostly an amorphous component, the weight average molecular weight M _w AA is defined as the weight average molecular weight of fraction 1.

1-4. Other properties of propylene-ethylene copolymer (A) The content of component (AC) in propylene-ethylene copolymer (A) is 10 with respect to the total amount of propylene-ethylene copolymer (A). ~ 98 wt%. Preferably it is 30 to 95 weight%, More preferably, it is 50 to 90 weight%. Correspondingly, the range of the component (AA) is 2 to 90% by weight with respect to the total amount of the propylene-ethylene copolymer (A). Preferably it is 5-70 weight%, More preferably, it is 10-50 weight%. If the content of the component (AA) is below this range, the effect as a modifier is insufficient, and if it exceeds, the fluidity of the particles of the copolymer (A) itself deteriorates, making it difficult to handle industrially. It is not preferable.

The MFR of the propylene-ethylene copolymer (A) of the present invention at 230 ° C. and 2.16 kg load is 10 g / 10 min. That is necessary. Preferably 13 g / 10 min. More preferably, 15 g / 10 min. That's it. Below this, the fluidity is inferior. There is no need to specify the upper limit, but 500 g / 10 min. If it exceeds 1, the production and molding may be difficult.
The melting point by DSC of the propylene-ethylene copolymer (A) of the present invention is characterized by being 150 ° C. or higher. Those below this are inferior in heat resistance. There is no particular need to define the upper limit of the melting point, but those exceeding 180 ° C. are practically difficult to produce.

In the propylene-ethylene copolymer (A) of the present invention, it is necessary that the component (AA) MFRA-2 and the weight average molecular weight M _w AA have the following relationship.
log (MFRA-2) ≦ −3.9 × log (MwA−A) +20.4 (Expression 1)
Here, MFRA-2 is obtained by the following formula 1 ', MFRA-1 of the crystalline polypropylene component polymerized in the first stage and MFRA of the entire propylene-ethylene copolymer (A) and (AC ) And (AA) are obtained by a logarithmic additivity rule.
log (MFRA) = {weight% of component (AC)} / 100 × log (MFRA-1) + {weight% of component (AA)} / 100 × log (MFRA-2) (( Formula 1 ')

  In general polypropylene resins, it is well known to those skilled in the art that the logarithm of MFR and the logarithm of weight average molecular weight satisfy a linear relationship. That is, satisfying this rule indicates that the fluidity of the copolymer component is low in proportion to the weight average molecular weight obtained by GPC measurement. In general, such a phenomenon that the MFR is reduced with respect to the apparent average molecular weight obtained from GPC, that is, the viscosity is improved, can be explained as an effect of introducing a branched structure into the molecule. That is, satisfying this rule represents the effect of introducing a branched structure into the copolymer portion.

In the propylene-ethylene copolymer (A) of the present invention, a graft copolymer (a kind of branched structure) composed of a crystalline polypropylene component and a propylene-ethylene random copolymer component is considered to be present. Will be described later.
At this time, with respect to the weight average molecular weight M _w A-A, if the value is too low, the impact resistance is inferior, and if it is too high, the fluidity is poor or the appearance deteriorates due to the generation of gel. The preferred range is 10,000 to 1,500,000.

1-5. Additional properties of propylene-ethylene copolymer (A) 1-5-1. Particle size of dispersed phase The propylene-ethylene copolymer (A) is a crystalline polypropylene phase in which the propylene-ethylene copolymer phase is present in the form of islands as the dispersed phase. Particle diameter: It is preferably 0.01 μm or more and 0.5 μm or less. More preferably, they are 0.05 micrometer or more and 0.4 micrometer or less. Above this range, the impact resistance is poor. Those below are difficult to manufacture. It is well known that the number average area equivalent circular particle system of a propylene-ethylene block copolymer polymerized using a general Ziegler-Natta catalyst or metallocene catalyst (which does not generate a branched structure) is several microns. The propylene-ethylene copolymer (A) disclosed in the present invention is characterized in that the particle size of the dispersed phase is extremely small.

The propylene-ethylene copolymer (A) according to the present invention includes a graft copolymer composed of a crystalline polypropylene component and a propylene-ethylene copolymer component. Although the details will be described later, it is considered that the factor that the propylene-ethylene copolymer according to the present invention exhibits good impact resistance can be attributed to the presence of the graft copolymer. In general, a polymer having a part composed of a chain of different monomers in one molecule, such as a real block copolymer or a graft copolymer, is a molecule that is considerably smaller than an ordinary phase separation structure, called a microphase separation structure. It is known to take a phase separation structure on the order of level, and such a fine phase separation structure significantly improves impact resistance.
The number average area equivalent circular particle diameter of the EPR block is determined by observation with a scanning electron microscope, a transmission electron microscope, an optical microscope, or the like. The area of the particles derived from the EPR block in the observation image is obtained, and converted to the diameter of an area equivalent circle to obtain the dispersed particle diameter. The observation visual field is determined so that 100 or more dispersions can be detected, and the number average area equivalent circle particle diameter of the EPR block is calculated from the dispersion particle diameters of 100 or more dispersions. In the evaluation of the particle diameter, a commercially available image analysis apparatus can be used.
In addition, in the observation of the particle diameter, if the amount of the component (AA) is too much, the amount of the dispersed phase component becomes too large in the observation field and it becomes difficult to identify the particle size. Is preferably carried out for those polymerized under conditions of about 10 to 30% by weight. That is, when the component (AA) content in the component (A) to be used exceeds 30% by weight, the polymerization balance is changed using the same catalyst system, and the above (AA) content is obtained. It is preferable to separately produce such a polymer and observe the particle diameter thereof.

1-5-2. Viscoelastic properties When the particle size of the dispersed phase is extremely small, see, for example, the Journal of Fiber Science, vol. 54 p. 391 (1998), which is introduced as relaxation of micelles, a long-time relaxation mode corresponding to the relaxation of the position between the dispersed phases of the polymer is likely to occur. Etc. can also be confirmed indirectly. Specifically, using a dynamic viscoelasticity measuring device such as ARES manufactured by TA Instruments Inc., using a parallel plate or cone plate geometry, and at a temperature of 200 ° C., frequency insertion of propylene-ethylene copolymer. A test is performed to measure the storage elastic modulus G ′ and the loss elastic modulus G ″.
In the case of a normal resin, particularly a resin having a high MFR and high fluidity as disclosed in the present invention, a relaxation mode of a resin called a termination region (or a flow region) on the low frequency side in this measurement mode is present G ′ is a square of the angular frequency and G ″ is a dependence close to the square of the angular frequency, and the resin does not show an elastic response, indicating a relationship of G ″> G ′. On the other hand, when there is a special long-time relaxation in the resin as in the micelle relaxation mode described above, the influence is particularly significant on G ′, and this magnitude relationship may be reversed.
A propylene-ethylene block copolymer polymerized using a general Ziegler-Natta catalyst or metallocene catalyst (which does not produce a graft copolymer), and has an MFR of 10 g / 10 min. If the above, G ″> G ′ at an angular frequency of 0.01 rad / s, the propylene-ethylene copolymer (A) including the graft copolymer according to the present invention has a long-term relaxation. Since it exists, G ′> G ″ is an additional feature.

1-6. Propylene-Ethylene Copolymer (A) Production Method The method for producing the propylene-ethylene copolymer (A) according to the present invention is preferably based on a continuous sequential polymerization method. After producing the crystalline propylene-based macromer, it is preferable to continuously produce the amorphous olefin copolymer successively. By sequentially polymerizing in such an order, a copolymer having a branched structure having a crystalline segment as a side chain and an amorphous segment as a main chain can be efficiently produced.

Further, the production method is not particularly limited by the catalyst component to be used, but using a polymerization catalyst obtained by contacting the following catalyst components (a), (b) and (c),
(I) first step of polymerizing propylene alone or propylene and other small amounts of ethylene and / or α-olefin; and (ii) polymerizing propylene with ethylene and / or α-olefin to produce ethylene or α- Propylene-ethylene copolymer (A) according to the present invention is produced with high productivity by a polymerization method having a second step of polymerizing 20 to 80% by weight of the total amount of olefin or ethylene and α-olefin with respect to all monomer components. can do.

(1) Component (a):
The catalyst component (a) used in the present invention is a metallocene compound having hafnium as a central metal represented by the following general formula (1).

[In General Formula (1), each of R ¹¹ and R ¹² independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 16 carbon atoms, a halogen-containing aryl group having 6 to 16 carbon atoms, or carbon. It represents a heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms, and at least one of R ¹¹ and R ¹² represents a heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms. Each of R ¹³ and R ¹⁴ is independently an aryl group having 6 to 16 carbon atoms, a halogen-containing aryl group having 6 to 16 carbon atoms, a silicon-containing aryl group having 6 to 16 carbon atoms, or 6 to 16 carbon atoms. Represents a heterocyclic group containing nitrogen, oxygen or sulfur. X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ¹¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, It represents a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

The heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms of R ¹¹ and R ¹² is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, or a substituted group. 2-furfuryl group, more preferably a substituted 2-furyl group.
Moreover, as a substituted 2-furyl group, a substituted 2-thienyl group, and a substituted 2-furfuryl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group, Examples thereof include halogen atoms such as fluorine atom and chlorine atom, alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group, and trialkylsilyl groups. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
Further, R ¹¹ and R ¹² are particularly preferably a 2- (5-methyl) -furyl group. R ¹¹ and R ¹² are preferably the same as each other.
R ¹³ and R ¹⁴ are preferably an aryl group having 6 to 16 carbon atoms, a halogen-containing aryl group having 6 to 16 carbon atoms, or a silicon-containing aryl group having 6 to 16 carbon atoms. In the range of 6 to 16, one or more hydrocarbon groups having 1 to 6 carbon atoms, silicon-containing hydrocarbon groups having 1 to 6 carbon atoms, halogen-containing carbon atoms having 1 to 6 carbon atoms on the aryl cyclic skeleton You may have a hydrogen group as a substituent.
At least one of R ¹³ and R ¹⁴ is preferably a phenyl group, a 4-tbutylphenyl group, a 2,3-dimethylphenyl group, a 3,5-ditbutylphenyl group, a 4-phenyl-phenyl group, or a chlorophenyl. Group, a naphthyl group, or a phenanthryl group, and more preferably a phenyl group, a 4-tbutylphenyl group, and a 4-chlorophenyl group. Moreover, the case where two R < ₂ > is mutually the same is preferable.

In General Formula (1), X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom. ˜20 silicon-containing hydrocarbon group, C 1-20 oxygen-containing hydrocarbon group, amino group, or C 1-20 nitrogen-containing hydrocarbon group. As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and s-butyl, vinyl, propenyl, Examples include alkenyl groups such as cyclohexenyl, arylalkyl groups such as benzyl, arylalkenyl groups such as trans-styryl, and aryl groups such as phenyl, tolyl, 1-naphthyl, and 2-naphthyl.
Specific examples of the oxygen-containing hydrocarbon group having 1 to 20 carbon atoms include alkoxy groups such as methoxy, ethoxy, propoxy and butoxy, allyloxy groups such as phenoxy and naphthoxy, arylalkoxy groups such as phenylmethoxy, and furyl groups. And oxygen-containing heterocyclic groups.
Specific examples of the nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms include alkylamino groups such as methylamino, dimethylamino, ethylamino and diethylamino, arylamino groups such as phenylamino and diphenylamino, (methyl) ( (Alkyl) (aryl) amino groups such as phenyl) amino, and nitrogen-containing heterocyclic groups such as pyrazolyl and indolyl.
In the halogenated hydrocarbon group having 1 to 20 carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenated hydrocarbon group is a compound in which, when the halogen atom is, for example, a fluorine atom, the fluorine atom is substituted at an arbitrary position of the hydrocarbon group. Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, and trichloromethyl groups.
Specific examples of the silicon-containing hydrocarbon group having 1 to 20 carbon atoms include trialkylsilylmethyl groups such as trimethylsilylmethyl and triethylsilylmethyl, dialkyl such as dimethylphenylsilylmethyl, diethylphenylsilylmethyl, and dimethyltolylsilylmethyl. (Alkyl) (aryl) silylmethyl group and the like can be mentioned.

In the general formula (1), Q ¹¹ couples the two five-membered ring, a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a hydrocarbon group having 1 to 20 carbon atoms silylene Group or germylene group. When two hydrocarbon groups exist on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermylene Examples include groups. In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.

Of the compounds represented by the general formula (1), preferred compounds are specifically exemplified below.
Dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-thienyl) -4-phenyl -Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2 -(5-Methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ] Hafnium, dichloro [1,1'-dimethylgermylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dic B [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5- Trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] hafnium dichloride, dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) ) -4-Phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2- (5-methyl-2-furyl) -4- Enyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-methyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2- (5-Methyl-2-furyl) -4-isopropyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furfuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5 -Methyl-2-furyl) -4- (4-fluorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-Methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4 -(4-t-butylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1 , 1′-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] hafni Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -(5-Methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- ( 2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1, 1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -(5-t-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (9-phenanthryl) -indenyl}] Hafnium, dichloro [1,1′-dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1 ′ -Dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, and the like. .

Of these, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethyl gel are more preferable. Mylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- ( 4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-naphthyl-indenyl}] hafnium, dichloro [1,1′-dimethyl Silylene bis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium.
Particularly preferred is dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2- (5-Methyl-2-furyl) -4-naphthyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t -Butylphenyl) -indenyl}] hafnium.

(2) Component (b):
Next, the catalyst component (b) used in the present invention is an ion-exchange layered silicate.

(I) Types of ion-exchange layered silicates In the present invention, ion-exchange layered silicates (hereinafter sometimes simply referred to as silicates) are surfaces in which ionic bonds or the like are formed by a binding force. It refers to a silicate compound that has a crystal structure that is stacked in parallel and that allows the contained ions to be exchanged.
Most silicates are naturally produced mainly as the main component of clay minerals, and are generally dispersed / swelled in water and purified by differences in sedimentation rate, etc., but they can be completely removed. Although it may be difficult and contains impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicate, they may be included. Depending on the type, amount, particle size, crystallinity, and dispersion state of these impurities, it may be preferable to pure silicate, and such a complex is also included in component (b).
In addition, the raw material of this invention refers to the silicate of the previous stage which performs the chemical treatment of this invention mentioned later. Further, the silicate used in the present invention is not limited to a natural product, and may be an artificial synthetic product.
In addition, in the present invention, if there is ion exchange properties before chemical treatment, the physical and chemical properties are changed by the treatment, and silicates having no ion exchange properties or layer structures are also included. Treated as an ion-exchanged layered silicate.

Specific examples of ion-exchanged layered silicates include layered silicates having a 1: 1 type structure or a 2: 1 type structure described in, for example, Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1988). Can be mentioned.
The 1: 1 type structure is based on the stacking of the 1: 1 layer structure in which one layer of tetrahedron sheet and one layer of octahedron sheet are combined as described in the above “clay mineralogy” and the like. The 2: 1 type structure is a structure based on a stack of 2: 1 layer structures in which two layers of tetrahedral sheets sandwich one layer of octahedral sheets.

Specific examples of ion-exchangeable layered silicates in which the 1: 1 layer is the main constituent layer include kaolin silicates such as dickite, nacrite, kaolinite, metahalloysite, halloysite, chrysotile, risardite, antigolite, etc. Examples include serpentine silicates.

Specific examples of ion-exchange layered silicates with 2: 1 layers as the main constituent layers include smectite group silicates such as montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, and vermiculite groups such as vermiculite. Examples thereof include mica group silicates such as silicate, mica, illite, sericite, and sea green stone, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group, and the like. These may form a mixed layer.

Among these, the main component is preferably an ion-exchange layered silicate having a 2: 1 type structure. More preferably, the main component is a smectite group silicate, and still more preferably, the main component is montmorillonite.
The type of interlayer cations (cations contained between the layers of the ion-exchange layered silicate) is not particularly limited, but as a main component, alkali metals of the first group of the periodic table such as lithium and sodium, calcium and magnesium Alkali earth metals of Group 2 of the periodic table, etc., or transition metals such as iron, cobalt, copper, nickel, zinc, ruthenium, rhodium, palladium, silver, iridium, platinum, gold, etc. are relatively It is preferable in that it can be easily obtained.

(II) Granulation of ion-exchangeable layered silicate The ion-exchangeable layered silicate may be used in a dry state or in a slurry state in a liquid. In addition, the shape of the ion-exchange layered silicate is not particularly limited, and may be a naturally produced shape, a shape when artificially synthesized, or a shape by operations such as pulverization, granulation, and classification. You may use the processed ion exchange layered silicate. Of these, the granulated ion-exchange layered silicate is particularly preferable because it gives good polymer particle properties when the ion-exchange layered silicate is used as a catalyst component.

Processing of the shape of the ion-exchange layered silicate such as granulation, pulverization, and classification may be performed before the chemical treatment (that is, the following chemical treatment is performed on the ion-exchanged layered silicate whose shape has been processed in advance). The shape may be processed after chemical treatment.
Examples of the granulation method used here include stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, fluidized bed granulation method, emulsion granulation method. , Submerged granulation method, compression molding granulation method, and the like, but are not particularly limited. Preferably, agitation granulation method, spray granulation method, rolling granulation method, and fluidized granulation method are exemplified, and particularly preferably, agitation granulation method and spray granulation method are exemplified.
When spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, and xylene is used as a dispersion medium for the raw slurry. Preferably, water is used as a dispersion medium. The concentration of the component (b) in the raw slurry liquid for spray granulation from which spherical particles are obtained is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight. . The inlet temperature of the hot air for spray granulation from which spherical particles are obtained varies depending on the dispersion medium, but is 80 to 260 ° C, preferably 100 to 220 ° C when water is taken as an example.

In granulation, in order to obtain a carrier having high particle strength and to improve propylene polymerization activity, the silicate is refined as necessary. The silicate may be refined by any method. As a method for miniaturization, either dry pulverization or wet pulverization is possible. Preferably, wet pulverization using water as a dispersion medium and utilizing the swellability of silicate, for example, a method using forced stirring using polytron or the like, a method using dyno mill, pearl mill, or the like. The average particle size before granulation is 0.01 to 3 μm, preferably 0.05 to 1 μm.
Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation. Examples of the binder used include magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycols and the like.
The spherical particles obtained as described above preferably have a compression fracture strength of 0.2 MPa or more in order to suppress crushing and fine powder generation in the polymerization step. The particle size of the granulated ion-exchange layered silicate is in the range of 0.1 to 1000 μm, preferably 1 to 500 μm. There is no particular limitation on the pulverization method, and either dry pulverization or wet pulverization may be used.

(III) Chemical treatment of ion-exchange layered silicate The ion-exchange layered silicate of the catalyst component (b) according to the present invention can be used as it is without any particular treatment, but it is desirable to perform the chemical treatment. The chemical treatment of the ion-exchange layered silicate refers to bringing an acid, salt, alkali, organic substance or the like into contact with the ion-exchange layered silicate.

A common effect of chemical treatment is to exchange interlayer cations. In addition, various chemical treatments have the following various effects. For example, according to the acid treatment with acids, impurities on the silicate surface can be removed and the surface area can be increased by eluting cations such as Al, Fe, and Mg in the crystal structure. This contributes to increasing the acid strength of the silicate and increasing the amount of acid sites per unit weight.
In alkali treatment with alkalis, the crystal structure of the clay mineral is destroyed, resulting in a change in the structure of the clay mineral.
Below, the specific example of a processing agent is shown. In the present invention, a combination of the following acids and salts may be used as the treating agent. Moreover, the combination of these acids and salts may be sufficient.

(I) Acids In addition to removing impurities on the surface or exchanging cations existing between layers, the acid treatment is carried out in part or all of cations such as Al, Fe and Mg incorporated in the crystal structure. Can be eluted. Examples of the acid used in the acid treatment include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, benzoic acid, stearic acid, propionic acid, acrylic acid, maleic acid, fumaric acid, and phthalic acid. Of these, inorganic acids are preferable, sulfuric acid, hydrochloric acid and nitric acid are preferable, and sulfuric acid is more preferable.

(Ii) Salts Salts are composed of a cation selected from the group consisting of an organic cation, an inorganic cation, and a metal ion, and an anion selected from the group consisting of an organic anion, an inorganic anion, and a halide ion. Examples of such salts are exemplified. For example, at least one selected from the group consisting of a cation containing at least one atom selected from Groups 1 to 14 of the periodic table, a halogen anion, an inorganic Bronsted acid, and an organic Bronsted acid anion. A preferred example is a compound composed of an anion.

Specific examples of such salts include LiCl, LiBr, Li ₂ SO ₄ , Li ₃ (PO ₄ ), LiNO ₃ , Li (OOCCH ₃ ), NaCl, NaBr, Na ₂ SO ₄ , and Na ₃ (PO ₄ ). , NaNO ₃ , Na (OOCCH ₃ ), KCl, KBr, K ₂ SO ₄ , K ₃ (PO ₄ ), KNO ₃ , K (OOCCH ₃ ), CaCl ₂ , CaSO ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , Ti (OOCCH ₃ ) ₄ , MgCl ₂ , MgSO ₄ , Mg (NO ₃ ) ₂ , Mg ₃ (C ₆ H ₅ O ₇ ) ₂ , Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , TiBr ₄ , TiI ₄ , Zr (OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , ZrF ₄ , ZrCl _{4 and the} like.
Also, Cr (OOCH ₃ ) ₂ OH, Cr (CH ₃ COCHCOCH ₃ ) ₃ , Cr (NO ₃ ) ₃ , Cr (ClO ₄ ) ₃ , CrPO ₄ , Cr ₂ (SO ₄ ) ₃ , CrO ₂ Cl ₃ , CrF ₃ , CrCl ₃ , CrBr ₃ , CrI ₃ , FeCO ₃ , Fe (NO ₃ ) ₃ , Fe (ClO ₄ ) ₃ , FePO ₄ , FeSO ₄ , Fe ₂ (SO ₄ ) ₃ , FeF ₃ , FeCl ₃ , MnBr ₃ FeI ₃ , FeC ₆ H ₅ O ₇ , Co (OOCH ₃ ) _{2 and the} like.
Furthermore, CuCl ₂ , CuBr ₂ , Cu (NO ₃ ) ₂ , CuC ₂ O ₄ , Cu (ClO ₄ ) ₂ , CuSO ₄ , Cu (OOCCH ₃ ) ₂ , Zn (OOCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , ZnBr ₂ , ZnI ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ , Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO _{4 and the} like.
Among these, a compound in which the anion is composed of an inorganic Bronsted acid or a halogen and the cation is composed of Li, Mg, or Zn is preferable.
Particularly preferred compounds of such salts include LiCl, Li ₂ SO ₄ , MgCl ₂ , MgSO ₄ , ZnCl ₂ , ZnSO ₄ , Zn (NO ₃ ) ₂ , Zn ₃ (PO ₄ ) ₂ .

(Iii) Other treatment agents In addition to the acid and salt treatment, the following alkali treatment or organic matter treatment may be performed as necessary. Examples of the treatment agent in the alkali treatment include LiOH, NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , Ba (OH) _{2 and the} like.
Examples of organic treating agents include trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, dodecylammonium, N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,5- Examples thereof include, but are not limited to, pentamethylanilinium, N, N-dimethyloctadecylammonium, and octadodecylammonium.
Moreover, these processing agents may be used independently and may be used in combination of 2 or more types. These combinations may be used in combination for the treatment agent added at the start of the treatment, or may be used in combination for the treatment agent added during the treatment. The chemical treatment can be performed a plurality of times using the same or different treatment agents.

(Iv) Chemical treatment conditions The various treatment agents described above may be dissolved in an appropriate solvent and used as a treatment solution, or the treatment agent itself may be used as a solvent. Although there is no restriction | limiting in particular as a solvent which can be used, Water and alcohol are common, and water is especially preferable. For example, when performing acid treatment as a chemical treatment, by controlling acid treatment conditions such as acid treatment agent concentration, ratio of ion-exchange layered silicate and treatment agent, treatment time, treatment temperature, etc., an ion layered silicate compound Can be controlled by changing to a predetermined composition and structure.

Regarding such an acid treating agent concentration, it is preferable to treat with an acid having an acid concentration (N) satisfying the following formula.
N ≧ 1.0
The acid concentration N shown here is defined as the number of moles of acid × the valence of acid / the volume of the acid aqueous solution (unit: mole / liter). However, when a salt is allowed to coexist, the amount of water of crystallization contained in the salt compound is considered, but the volume change due to the salt is not considered. As for the specific gravity of the acid aqueous solution, the basic edition IIp6 (edited by the Chemical Society of Japan, published by Maruzen, revised 3rd edition) of the Chemical Handbook was cited. The upper limit of the acid concentration N is preferably 20 or less, particularly 15 or less, from the viewpoint of safety in handling, ease, and equipment.
The ratio between the ion-exchange layered silicate and the treatment agent is not particularly limited, but preferably, the ion-exchange layered silicate [g]: treatment agent [acid valence × mol number] = 1: 0.001. ˜1: About 0.1.
The acid treatment temperature is preferably in the range of room temperature to the boiling point of the treatment agent solution, the treatment time is selected from 5 minutes to 24 hours, and at least a part of the material constituting the ion-exchange layered silicate is It is preferable to carry out under the conditions for removal or replacement. The acid treatment conditions are not particularly limited, but when sulfuric acid is used as the chemical treatment, the treatment temperature is from 80 ° C. to the boiling point of the treating agent solvent and the treatment time may be from 0.5 hours to less than 5 hours. preferable.

(IV) Drying of ion-exchange layered silicate It is possible to remove the excessive treatment agent and ions eluted by the treatment after the chemical treatment is performed, which is preferable. At this time, generally, a liquid such as water or an organic solvent is used. After the dehydration, drying is performed. In general, the drying temperature can be 100 to 800 ° C, preferably 150 to 600 ° C. Exceeding 800 ° C. is not preferable because it may cause structural destruction of the silicate.
Since these ion-exchange layered silicates have different characteristics depending on the drying temperature even if they are not structurally destroyed, it is preferable to change the drying temperature depending on the application. The drying time is usually 1 minute to 24 hours, preferably 5 minutes to 4 hours, and the atmosphere is preferably dry air, dry nitrogen, dry argon, or under reduced pressure. It does not specifically limit regarding the drying method, It can implement by various methods.

(V) Composition after chemical treatment of ion-exchangeable layered silicate The chemical-treated ion-exchangeable layered silicate is 0.01% as the atomic ratio of Al / Si as the catalyst component (b) according to the present invention. It is preferably -0.25, preferably 0.03-0.24, more preferably 0.05-0.23. The Al / Si atomic ratio is considered to be an index of the acid treatment strength of the clay portion. In addition, as a method for controlling the Al / Si atomic ratio within the above range, there is a method in which montmorillonite is used as the ion-exchange layered silicate before chemical treatment and the chemical treatment described in (III) is performed. .
Aluminum and silicon in the ion-exchange layered silicate are measured by a method of preparing a calibration curve by a chemical analysis method by JIS method and quantifying with a fluorescent X-ray.

(3) Component (c):
The catalyst component (c) used in the present invention is an organoaluminum compound, and preferably an organoaluminum compound represented by the general formula (AlR _n X _3-n ) _m is used. In formula, R represents a C1-C20 alkyl group, X represents a halogen, hydrogen, an alkoxy group, or an amino group, n represents 1-3, m represents the integer of 1-2, respectively. The organoaluminum compounds can be used alone or in combination.

  Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride. Of these, trialkylaluminum and alkylaluminum hydride with m = 1 and n = 3 are preferable. More preferably, R is a trialkylaluminum having 1 to 8 carbon atoms.

(4) Preparation of catalyst:
The catalyst for olefin polymerization according to the present invention comprises the above component (a), component (b) and component (c). These may be contacted in the polymerization tank or outside the polymerization tank and preliminarily polymerized in the presence of olefin.
The olefin refers to a hydrocarbon having at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, divinylbenzene, and the like. There is no restriction | limiting, You may use the mixture of these and another olefin. An olefin having 3 or more carbon atoms is preferred, and propylene is more preferred.

The amount of component (a), component (b) and component (c) used in the present invention is arbitrary. For example, the amount of component (a) used relative to component (b) is preferably in the range of 0.1 μmol to 1000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of component (b). The amount of component (c) relative to component (a) is preferably a transition metal molar ratio of preferably 0.01 to 5 × 10 ⁶ , particularly preferably 0.1 to 1000.
In addition to the component (a), other types of complexes can be used as long as the substance of the present invention can be produced.
In this case, it is preferable to combine a metallocene compound capable of copolymerizing a terminal vinyl macromer with the catalyst component (a) and producing a high molecular weight polymer compared to the catalyst component (a). By combining them, a polymer having improved melt properties and mechanical properties, which are requirements of the present invention, can be obtained.
Examples of such a metallocene compound include a catalyst component (a-2) represented by the following general formula (2).

The compound represented by the general formula (2) is a metallocene compound, and in the general formula (2), Q ²¹ is a binding group that bridges two conjugated five-membered ring ligands, and has a carbon number. A divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms, or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted silylene group or a substituted germylene group. It is. The substituent bonded to silicon and germanium is preferably a hydrocarbon group having 1 to 12 carbon atoms, and two substituents may be linked. Specific examples include methylene, dimethylmethylene, ethylene-1,2-diyl, dimethylsilylene, diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylsilylene, diethylsilylene, Examples thereof include diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylgermylene, diethylgermylene, diphenylgermylene, methylphenylgermylene and the like.
Me is zirconium or hafnium, preferably hafnium.

Furthermore, X ²¹ and Y ²¹ are auxiliary ligands, which react with the cocatalyst of component (b) to generate active metallocene having olefin polymerization ability. Therefore, as long as this purpose is achieved, X ²¹ and Y ²¹ are not limited to the type of ligand, and each independently represents hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms is shown. .

In general formula (2), R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms. is there. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.
R ²³ and R ²⁴ each independently contains a halogen having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, or a plurality of hetero elements selected from these. A good aryl group. Preferable examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluorobiphenylyl), 4- (2-chlorobiphenylyl), 1-naphthyl, 2-naphthyl, 3,5-dimethyl-4-tert-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl Etc.

Non-limiting examples of the metallocene compound include the following.
For example, dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4-hydroazulenyl)} hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylene Bis {2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-t-butylphenyl) ) -4-Hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- ( -Methyl-4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl} ] Hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -Methyl-4- (1-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenyl) -4- Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-chloro-4-biphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2-methyl-4- (9-phenanthryl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl} ] Hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-n-propyl-] 4- (3-Chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro 1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-tert-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2-methyl -4- (2-fluoro-4-biphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl] }] Hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, and the like.

Moreover, when using another kind of catalyst component (a-2), the ratio of the amount of the catalyst component (a-2) to the total amount of the catalyst component (a) and the catalyst component (a-2) is propylene- Although it is arbitrary as long as the characteristics of the ethylene copolymer (A) are satisfied, it is possible to adjust the balance between melt physical properties and catalyst activity by changing this ratio.
That is, from the component (a), a low molecular weight terminal vinyl macromer is generated, and from the component (a-2), a high molecular weight body obtained by copolymerizing a part of the macromer is generated. Therefore, by increasing the proportion of component (a), it is possible to obtain a propylene-ethylene copolymer with improved mechanical properties such as impact resistance, which is an effect of the present invention. Therefore, the ratio of the amount of the catalyst component (a-2) to the total amount of the catalyst component (a) and the catalyst component (a-2) is 0.7 or less, more preferably 0.6 or less, particularly preferably 0.5. It is as follows.
Further, the propylene-ethylene copolymer defined in the present invention preferably has a high fluidity when used for injection molding. For this purpose, it is preferable to reduce the effect of the presence of the graft copolymer on the viscoelasticity, that is, λmax is less than 2.0.
It is possible to reduce λmax by, for example, reducing the number of grafts by reducing the amount of propylene macromer. For this purpose, the ratio of the amount of the catalyst component (a-2) to the total amount of the catalyst component (a) and the catalyst component (a-2) is preferably 0.15 or more, more preferably 0.25 or more, particularly Preferably, control is possible by setting it to 0.3 or more.

  The order of contacting the component (a), the component (b) and the component (c) is arbitrary, and after contacting two of these components, the remaining one component may be contacted, The components may be contacted simultaneously. In these contacts, a solvent may be used for sufficient contact. Examples of the solvent include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic unsaturated hydrocarbons, halides thereof, and prepolymerized monomers. Specific examples of the aliphatic saturated hydrocarbon and the aromatic hydrocarbon include hexane, heptane, toluene and the like. Further, as a prepolymerized monomer, propylene can be used as a solvent.

(5) Prepolymerization As mentioned above, it is preferable that the catalyst according to the present invention is subjected to a prepolymerization treatment consisting of a small amount of polymerization by bringing an olefin into contact therewith. The olefin used is not particularly limited, but as described above, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcyclohexane. Examples include alkanes and styrene. The olefin feed method may be any method such as a feed method for maintaining the olefin at a constant rate or a constant pressure in the reaction tank, a combination thereof, or a stepwise change.

The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. Further, the prepolymerization amount is preferably 0.01 to 100, more preferably 0.1 to 50, by weight ratio of the prepolymerized polymer to the component (b). Further, the component (c) can be added or added during the prepolymerization.
A method of coexisting a polymer such as polyethylene or polypropylene and a solid of an inorganic oxide such as silica or titania at the time of contacting or after the contact of the above components is also possible.
The catalyst may be dried after the prepolymerization. The drying method is not particularly limited, and examples thereof include reduced-pressure drying, heat drying, and drying by circulating a drying gas. These methods may be used alone or in combination of two or more methods. May be. In the drying step, the catalyst may be stirred, vibrated, fluidized, or allowed to stand.

1-7. DETAILED DESCRIPTION OF THE POLYMERIZATION METHOD As long as the olefin polymerization catalyst comprising the component (a), the component (b) and the component (c) and the monomer efficiently contact with each other, any form can be adopted as the polymerization form. Specifically, a slurry method using an inert solvent, a bulk polymerization method using propylene as a solvent without substantially using an inert solvent, or a gas phase polymerization method for maintaining each monomer in a gaseous state without using a liquid solvent. Etc. can be adopted.

As the polymerization method, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied.
In addition, the number of polymerization stages is not particularly limited as long as the substance of the present invention can be produced, but a mode such as two stages of bulk polymerization, gas phase polymerization after bulk polymerization, two stages of gas phase polymerization, and two stages of slurry is also possible. Further, it can be produced with a larger number of polymerization stages.
In order to produce the material disclosed in the present invention, a crystalline propylene macromer having a high vinyl end is produced in the first step and copolymerized with propylene and ethylene and / or α-olefin in the second step. It is necessary. By successively polymerizing sequentially in such an order, the crystalline propylene-based macromer produced in the first step is copolymerized in the second step, has a crystalline segment in the side chain, and the main chain is amorphous. The polymer of the present invention having a branched structure having segments can be produced.
In order to obtain the compound disclosed in the present invention, the first step is performed by bulk polymerization and the second step is performed by gas phase polymerization, or both the first step and the second step are performed by gas phase polymerization. Is preferred. The reason for this is that the environmental load due to the fact that no solvent is substantially used can be reduced, and that the manufacturing process can be simplified.

1-7-1. First Step In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene or the like is used alone or as a polymerization solvent. The polymerization temperature is 0 to 150 ° C., and hydrogen can be used supplementarily as a molecular weight regulator. The polymerization pressure is suitably from 0 to 3 MPaG, preferably from 0 to 2 MPaG.
In the case of the bulk polymerization method, the polymerization temperature is 0 to 80 ° C, preferably 60 to 80 ° C, more preferably 65 to 75 ° C. The polymerization pressure is 0 to 5 MPaG, preferably 0 to 4 MPaG.
In the case of gas phase polymerization, the polymerization temperature is 0 to 200 ° C, preferably 60 to 120 ° C, more preferably 70 to 100 ° C. The polymerization pressure is suitably from 0 to 4 MPaG, preferably from 0 to 3 MPaG.
It is considered that the crystalline propylene macromer produced in this step is partially copolymerized at the same time to produce a polymer having a branched structure in which both side chains of the main chain have crystalline propylene polymerized segments.

Further, the propylene-ethylene copolymer defined in the present invention preferably has a high fluidity particularly in the injection molding application. For this purpose, it is preferable to reduce the effect of the presence of the graft copolymer on the viscoelasticity, that is, λmax is less than 2.0.
It is possible to reduce λmax, for example, by reducing the length of the graft chain by reducing the molecular weight of the crystalline propylene macromer produced in the first step.
Methods for reducing the molecular weight include lowering the monomer concentration (pressure) during polymerization, increasing the polymerization temperature, and using hydrogen as a molecular weight regulator, and these methods can be controlled in combination. For example, λmax can be controlled by setting the polymerization temperature to 75 ° C. or higher, or using hydrogen as a molecular weight regulator.

1-7-2. Second Step In the case of gas phase polymerization, the polymerization temperature is 20 to 90 ° C, preferably 30 to 80 ° C, and more preferably 50 to 80 ° C. In addition, hydrogen can be used supplementarily as a molecular weight regulator. The polymerization pressure is suitably 0.5-4 MPaG, preferably 0.5-3 MPaG.

Here, the crystalline propylene polymerized macromer produced in the first step is copolymerized to produce a copolymer having a crystalline propylene polymerized segment as a side chain and an amorphous propylene copolymerized segment in the main chain. Can be considered.
The ease of copolymerization (copolymerizability) of this macromer depends on the polymerization temperature, and the polymerization temperature is preferably relatively high in order to increase the copolymerizability. Therefore, in the present invention, a copolymer having a crystalline propylene polymer segment as a side chain and an amorphous propylene copolymer segment as a main chain (so-called graft copolymer) is efficiently produced, and thereby the dispersed phase is refined. In order to obtain a polymer having an effect, the polymerization temperature is preferably 60 ° C. or higher, more preferably 70 ° C. or higher.

When ethylene is used as the comonomer, a desired polymer having an ethylene content of 20 to 80% by weight can be produced by controlling the gas phase ethylene gas composition. Here, the produced (non-crystalline) propylene-ethylene random propylene copolymer is partially copolymerized with a low vinyl terminal content, and both the main chain and the side chain are (non-crystalline) propylene-ethylene random It is considered that a polymer having a branched structure having a copolymerized segment is formed.
In this case, the higher the propylene content in the amorphous propylene-ethylene random copolymer, the higher the vinyl end content. That is, by increasing the ethylene content in the amorphous propylene-ethylene random copolymer, it is possible to reduce the λmax of the copolymer.
For example, in order to produce an amorphous propylene-ethylene copolymer having an ethylene content of 40 to 60% by weight, it is necessary to control the ethylene gas composition in the gas phase to 50 mol% or more, preferably 60 mol%. % Or more, more preferably 65 mol% or more. Moreover, regarding an upper limit, it is 90 mol% or less, Preferably it is 87 mol% or less, More preferably, it is 85 mol% or less.
In order to produce an amorphous propylene-ethylene copolymer having an ethylene content of 20 to 40% by weight, it is necessary to control the ethylene gas composition in the gas phase to 20 mol% or more, preferably 25 mol % Or more, more preferably 30 mol% or more. The upper limit is 65 mol% or less, preferably 60 mol% or less, and more preferably 50 mol% or less.

Further, the propylene-ethylene copolymer defined in the present invention preferably has a high fluidity particularly in the injection molding application. For this purpose, it is preferable to reduce the effect of the presence of the graft copolymer on the viscoelasticity, that is, λmax is less than 2.0.
It is possible to reduce λmax, for example, by reducing the number of branches per polymer chain by reducing the molecular weight of the amorphous main chain produced in the second step.
Methods for reducing the molecular weight of the non-crystalline main chain include lowering the monomer concentration (pressure) during polymerization, increasing the polymerization temperature, and using hydrogen as a molecular weight regulator. It can be controlled by combining.
In the case of gas phase polymerization, a method in which the polymerization temperature is relatively high can be considered. For example, by setting the polymerization temperature to 70 ° C. or higher, it is possible to control both λmax and dispersion phase refinement.

1-8. Consideration on the structure of the propylene-ethylene copolymer (A) As described above, a part of the crystalline propylene polymer produced in the first stage is present in a state in which a reaction is terminated in the state of a terminal vinyl group. When the second-stage polymerization is carried out as it is, the terminal vinyl crystalline propylene polymer is a macromonomer, involved in the second-stage polymerization, the propylene-ethylene random copolymer component is the main chain, and the crystalline A graft copolymer in which the propylene polymer component is a side chain is formed. Therefore, the propylene-ethylene copolymer (A) according to the present invention does not simply consist of a crystalline polypropylene component and a propylene-ethylene copolymer component, but additionally contains the above graft copolymer component. It is a waste. In other words, strictly speaking, the component manufactured in the first stage and the component (AC), and the component manufactured in the second stage and the component (AA) are different components.

The graft copolymer is presumed to exist mainly at the interface between the crystalline polypropylene component and the propylene-ethylene copolymer component due to thermodynamic requirements. As a result, it plays the role which reduces the interface free energy between both components, and it is estimated that a propylene-ethylene copolymer component disperses finely.
As described above, the presence or absence of such a graft copolymer can be indirectly confirmed by the relationship between the MFR and the weight average molecular weight, or by making the dispersed phase finer by observing the structure.

As one of the methods for determining whether or not a graft copolymer in which the propylene-ethylene random copolymer component as described above is a main chain and the crystalline propylene polymer component is a side chain is usually present It is effective to use the strain hardening degree (λmax) obtained from the measurement of the extensional viscosity. However, if the degree of strain hardening is too high, the effect of branching on the viscoelastic properties becomes too strong, and the flow properties required particularly in injection molding applications deteriorate. Therefore, in the propylene-ethylene copolymer (A) according to the present invention, λmax is preferably less than 2.
The propylene-ethylene copolymer (A) according to the present invention exhibits the effect of refining the dispersed phase while λmax is less than 2. This means that although the effect of the presence of the graft copolymer on the extensional viscosity characteristics is reduced by improving the fluidity, that is, by reducing the molecular weight, the effect of refining the dispersed phase is retained. In particular, it can be said that this is a preferable characteristic in an injection molding application that strongly requires fluidity.

  Here, regarding the method for measuring the strain hardening degree, the same value can be obtained in principle by any method as long as the uniaxial extensional viscosity can be measured. For example, the details of the measurement method and the measurement device include the method described in Polymer 42 (2001) 8663 of publicly known literatures. Preferred measurement methods and measurement devices include the following.

Measuring method 1:
Apparatus: Ales manufactured by Rheometrics
Jig: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
Preparation of test piece: A sheet of 18 mm × 10 mm and a thickness of 0.7 mm is formed by press molding.

Measurement method 2:
Apparatus: Toyo Seiki Co., Ltd., Melten Rheometer
Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
Preparation of test piece: Extruded strands are prepared at a speed of 10 to 50 mm / min using an orifice with an inner diameter of 3 mm at 180 ° C. using a Capillograph manufactured by Toyo Seiki Co., Ltd.

Calculation method:
The elongational viscosity at a strain rate of 0.1 / sec is plotted as a log-log graph of time t (seconds) on the horizontal axis and elongational viscosity ηE (Pa · seconds) on the vertical axis. On the logarithmic graph, the viscosity immediately before strain hardening is approximated by a straight line, the maximum value (ηmax) of the extensional viscosity ηE until the amount of strain reaches 4.0 is obtained, and on the approximate straight line up to that time Let ηlin be the viscosity. ηmax / ηlin is defined as λmax and is used as an index of strain hardening degree.
The elongational viscosity and strain hardening degree calculated from the measuring method 1 and the measuring method 2 are, in principle, for measuring the inherent extensional viscosity and strain hardening degree of the substance and exhibit the same value. Therefore, either measurement method 1 or measurement method 2 may be used.

However, the measurement method 2 has a measurement restriction that a measurement sample hangs down when the molecular weight is relatively low (that is, when MFR> 2), and the measurement accuracy is lowered. In measurement method 1, when measuring a relatively high molecular weight (MFR <1), the measurement sample is deformed in a non-uniform manner, and distortion occurs at the time of measurement. There is a problem of measurement accuracy that is averaged and the strain hardening degree is estimated to be small.
Therefore, it is preferable for convenience to use the measuring method 1 for those having a low molecular weight and the measuring method 2 for those having a high molecular weight.
In the propylene-ethylene copolymer (A) according to the present invention in which the presence or absence of the graft copolymer with such extensional viscosity characteristics cannot be determined, as described above, the relationship between MFR and the weight average molecular weight, The presence of the graft copolymer can be indirectly confirmed by refining the dispersed phase by structure observation.

2. Propylene-ethylene copolymer component (B)
The propylene-ethylene copolymer component (B), which is the main component of the propylene-based resin composition of the present invention, is obtained by a continuous multi-stage process using a conventionally known Ziegler-Natta catalyst or metallocene catalyst. It is a propylene-ethylene copolymer obtained by polymerizing crystalline polypropylene in a stage and polymerizing a propylene-ethylene random copolymer component in the second stage and thereafter. It is also called union.

The component (B) can be produced by, for example, a slurry polymerization method, a gas phase polymerization method, or a liquid phase bulk polymerization method using a Ziegler-based highly stereoregular catalyst. It is preferable to produce by a legal method. As a polymerization method, either batch polymerization or continuous polymerization can be adopted, but it is preferable to produce by polymerization.
When producing this component (B), first, a crystalline propylene homopolymer part is formed by homopolymerization of propylene, and then an ethylene / propylene random copolymer part is formed by random copolymerization of propylene and ethylene. Although it is preferable from the standpoint of quality, carbon such as ethylene, 1-butene, 1-hexene, 1-octene, etc. is used as a comonomer within a range of several percent at the time of the initial polymerization as necessary unless it departs from the gist of the present invention. An α-olefin other than the number 3 may be copolymerized, or an α-olefin having 4 or more carbon atoms such as 1-butene, 1-hexene, and 1-octene may be copolymerized in two or more stages of polymerization.

As a specific production method, if it is a Ziegler catalyst, a titanium trichloride catalyst composed of titanium trichloride and an organoaluminum halide, a solid catalyst containing magnesium chloride, titanium halide, and an electron donating compound as essential components A method using a magnesium-supported catalyst composed of a component, organoaluminum and organosilicon compound, or a combination of an organoaluminum compound and a solid catalyst component formed by contacting organoaluminum and an organosilicon compound with a solid catalyst component The catalyst can be used for homopolymerization of propylene and then random copolymerization of propylene and ethylene.
As long as the metallocene-based catalyst satisfies various physical properties necessary for the component (B), a conventionally known metallocene-based catalyst capable of obtaining a high melting point polypropylene can be used without particular limitation. Illustratively, the catalyst component (a-2) can be raised among the catalyst components used in the production of the component (A), but it is not limited to this, and the high melting point is not produced without generating a terminal vinyl structure. Any catalyst system capable of producing a polypropylene resin can be employed. The selection of the central metal, simple substance, etc. can also be adopted without limiting a conventionally known method, but preferred examples have already been described in the description of the component (A).
In addition, the propylene-ethylene block copolymer can be used within the range that does not significantly impair the essence of the present invention, for example, other unsaturated compounds, for example, α-olefins such as 1-butene, vinyl esters such as vinyl acetate, and maleic anhydride. It may be a ternary or higher copolymer containing an unsaturated organic acid such as an acid or a derivative thereof, or a mixture thereof.

2-1. Composition of Component (B) Component (B) is the main component in the present invention, and is a component (mainly composed of crystalline polypropylene, which is fractionated and quantified by a temperature-programmed crystalline fractionation method from the balance between rigidity and impact resistance ( The amount of B-C) is 50 to 95% by weight based on the entire propylene-ethylene copolymer (B), and the amount of the component (BA) mainly composed of a propylene-ethylene random copolymer is propylene. -It is required that it is 5 to 50 weight% with respect to the whole ethylene copolymer (B). When the amount of the component (BA) is below this range, the impact resistance is inferior, and when it exceeds, the rigidity and heat resistance are inferior. Preferably it is 7 to 45 weight%, More preferably, it is 10 to 40 weight%.

2-2. Melting point of component (B) The propylene-ethylene copolymer (B) according to the present invention is characterized in that the melting point by DSC is 155 ° C or higher. Those below this are inferior in heat resistance. Preferably it is 156 degreeC or more, More preferably, it is 160 degreeC or more. There is no particular need to define the upper limit of the melting point, but those exceeding 180 ° C. are practically difficult to produce.

2-3. Relationship between MFR of component (B) and weight average molecular weight In component (B), the melt flow rate MFRB-2 of the component polymerized in the second stage and the weight average molecular weight M _w B-A of (BA) are It is necessary to be in the relationship of the following formula 2.
log (MFRB-2)> − 3.9 × log (MwB−A) +20.4 (Expression 2)
Here, MFRB-2 is obtained by the following formula 2 ′, MFRB-1 of the crystalline polypropylene component polymerized in the first stage and MFRB of the entire propylene-ethylene copolymer (B) and (BC ) And (B-A) is obtained by a logarithmic additive rule.
log (MFRB) = {weight% of component (BC)} / 100 × log (MFRB-1) + {weight% of component (BA)} / 100 × log (MFRB-2) (...) Formula 2 ′)
Considering the comparison with component (A), satisfying this rule means that there is no branched structure in component (B) that significantly changes the relationship between the weight average molecular weight and MFR. That is, it can be said to be a general feature of a propylene-ethylene copolymer polymerized by a conventionally known Ziegler-based or metallocene-based catalyst.
At this time, with respect to the weight average molecular weight M _w B-A, if the value is too low, the impact resistance is inferior, and if it is too high, the fluidity is poor or the appearance deteriorates due to the generation of gel. The preferred range is 10,000 to 1,500,000.
Incidentally, the (B-C), measured by the amount ratio and _{MFRB, MFRB-1, M w} B-A , etc. are already similar to the described components (A) Method of (B-A), to be determined .

2-4. Additional properties of component (B) 2-4-1. MFRB
The range of MFR (MFRB) of the propylene-ethylene copolymer (B) is 0.5 to 1000 g / 10 min. Is preferred. Outside this range, molding such as injection molding becomes difficult. A preferred range is 1 to 500 g / 10 min. And more preferably 10 to 300 g / 10 min. It is.

2-4-2. Ethylene content in component (BA) The ethylene content of the component (BA) is preferably 10 to 90% by weight based on the total amount of monomers in the component (BA). Those outside this range are inferior in impact resistance. Preferably it is 20 to 80 weight%, More preferably, it is 30 to 70 weight%. The ethylene content in component (BA) is quantified by the same method as described for component (AA).

2-4-3. Dispersion Phase Particle Size The propylene-ethylene copolymer (B) is a general copolymer that does not contain a special structure such as a graft copolymer inside, unlike the propylene-ethylene copolymer (A). is there. Accordingly, the particle size of the dispersed phase is larger than that of the propylene-ethylene copolymer (A).
The number average area equivalent circular particle diameter of the dispersed phase of the component (B) is characterized by being larger than 0.5 μm.
In addition, in the observation of the particle diameter, if the amount of the component (BA) is too much, the amount of the dispersed phase component is too large in the observation field and it becomes difficult to identify the particle size. Is preferably carried out for those polymerized under conditions of about 10 to 30% by weight. That is, when the component (B-A) content in the component (B) to be used exceeds 30% by weight, the polymerization balance is changed using the same catalyst system, and the above-mentioned (B-A) content is obtained. It is preferable to separately produce such a polymer and observe the particle diameter thereof.

2-4-4. Viscoelastic properties In component (B), no special long-term relaxation as observed in component (A) is observed, and thus the angular frequency 0.01 rad / It is a feature that G ″> G ′ in s.

3. Additional component (1) Additional component The following additional component can also be added to the propylene-based resin composition of the present invention.

(I) Elastomer Component In the present invention, the ethylene / α-olefin elastomer or styrene elastomer can be contained in the range of 0 to 40% by weight with respect to the total of 100% by weight of the propylene resin composition and the elastomer.
The ethylene / α-olefin elastomer and the styrene elastomer are used for the purpose of improving impact resistance and exhibiting good moldability, physical properties, and shrinkage characteristics.

Examples of the comonomer copolymerized with ethylene in the ethylene / α-olefin elastomer include α-olefins having 4 to 20 carbon atoms, such as 1-octene and 1-butene. No, it may be a mixture of two or more ethylene / α-olefin elastomers or styrene elastomers. The content of α-olefin in the ethylene / α-olefin-based elastomer is 10 to 60% by weight, preferably 20 to 50% by weight, and the density is 0.85 to 0.90 cm ³ , preferably 0.86 to 0.88 cm. ³ .
The styrene elastomer is a block or random copolymer of styrene and ethylene, propylene, 1-butene, butadiene, isoprene or the like, or a hydrogenated product thereof. The amount of bound styrene in the styrene elastomer is 5 to 45. wt%, and preferably 10 to 40 wt%, 0.88～0.95Cm ³ in density, preferably 0.89~0.92cm ^3.

The MFR of the elastomer component at 230 ° C. and a load of 2.16 kg is 0.1 to 20 g / 10 minutes, preferably 0.5 to 10 g / 10 minutes. When the MFR is less than 0.1 g / min, the moldability and paintability are poor, and when the MFR exceeds 20 g / 10 min, the impact resistance is inferior.
The ethylene / α-olefin-based elastomer can be produced by polymerization using a known titanium-based catalyst or metallocene catalyst. In the case of a styrene-based elastomer, it can be obtained by a usual anionic polymerization method and its polymer hydrogenation technique.
The blending amount of the ethylene / α-olefin elastomer and the styrene elastomer is 0 to 40% by weight, and preferably 3 to 35% by weight, particularly preferably 5 to 30% by weight in the case where the impact is emphasized. It is. When the amount of the ethylene / α-olefin copolymer elastomer exceeds 40% by weight, the rigidity and heat resistance of the propylene-based resin composition are significantly lowered, which is not preferable.

(Ii) Inorganic filler In this invention, an inorganic filler can be included in 0-40 weight% with respect to a total of 100 weight% of a propylene-type resin composition and an inorganic filler.
Examples of the inorganic filler used in the present invention include talc, wollastonite, calcium carbonate, barium sulfate, mica, glass fiber, carbon fiber, clay, and organic clay, and preferably talc, mica, glass fiber. Carbon fiber, particularly preferably talc. Talc is effective for improvement of rigidity, dimensional stability of a molded product, and adjustment thereof.

The particle size (including fiber diameter) of the inorganic filler varies depending on the inorganic compound used, but in the case of fibers, the fiber diameter is 3 to 40 μm, and in the case of granules, the particle diameter is about 1.5 to 150 μm. is there. In the case of talc, which is a suitable inorganic filler, the average particle size is preferably 1.5 to 40 μm, particularly preferably 2 to 15 μm. If the average particle size of talc is less than 1.5 μm, it aggregates and the appearance is reduced. On the other hand, if it exceeds 40 μm, the impact strength decreases, which is not preferable.
In the case of granular materials such as talc, in general, for example, talc ore is first pulverized with an impact pulverizer or micron mill pulverizer, or further pulverized with a jet mill or the like, and then with a cyclone or micron separator. Manufacture by classification adjustment method.
The talc may be surface-treated with various metal soaps, and so-called compressed talc having an apparent specific volume of 2.50 ml / g or less may be used.
The average particle size of the granular material is a value measured using a laser diffraction / scattering particle size distribution meter, and as a measuring device, for example, Horiba LA-920 type is preferable because of its excellent measurement accuracy. The fiber diameter of carbon fiber or glass fiber is generally calculated by cutting the fiber perpendicular to the fiber direction, observing the cross section under a microscope, measuring the diameter, and averaging 100 or more.
The blending amount of the inorganic filler in the resin is preferably 0 to 40% by weight, more preferably 3 to 35% by weight, and particularly preferably 5 to 30% by weight. When the amount of the inorganic filler exceeds 40% by weight, the impact resistance of the propylene-based resin composition is lowered, which is not preferable.

(2) Use of Other Components (i) Additives In order to further enhance the performance of the propylene-based resin of the present invention or to impart other performance to the propylene-based resin composition of the present invention, the present invention. Additives can also be blended within a range that does not impair the purpose.
As this additional component, a nucleating agent widely used as a compounding agent for polyolefin resin, a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, a neutralizer, a light stabilizer, an ultraviolet absorber, a lubricant Various additives such as antistatic agents, metal deactivators, peroxides, fillers, antibacterial agents, antifungal agents, fluorescent brighteners, colorants, and conductivity-imparting agents can be added.
The amount of these additives is generally 0.0001 to 5 parts by weight, preferably 0.001 to 3 parts by weight, based on 100 parts by weight of the composition.

(Ii) Use of other resins In order to further enhance the performance of the resin of the present invention or to impart other performance to the propylene resin composition of the present invention, within the range not impairing the object of the present invention. Other resin materials can also be blended.
As this additional component, LLDPE, LDPE, HDPE, modified polypropylene, polycarbonate, polyamide, modified PPE, etc. which are widely used as a compounding material for polyolefin resins can be added.
The amount of these resins is generally 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the composition.

(3) Production of propylene-based resin composition In the present invention, the above-described components, that is, the propylene-ethylene copolymer (A) and the propylene-ethylene copolymer (B) are optionally filled with an elastomer and an inorganic filler. Materials, other ingredients, etc. are blended at the blending ratios described above, and kneaded and produced using a conventional kneader such as a single screw extruder, twin screw extruder, Banbury mixer, roll mixer, Brabender plastograph, kneader. By granulating, the propylene-based resin composition of the present invention is obtained.
In this case, it is preferable to select a kneading and granulating method capable of improving the dispersion of each component, and it is usually performed using a twin-screw extruder. During the kneading and granulation, the above-mentioned components may be kneaded simultaneously or sequentially. Further, it is possible to adopt a method in which each component is divided and kneaded to improve performance.

(4) Use of propylene-based resin composition The propylene-based resin composition of the present invention has a sufficiently improved balance of rigidity, heat resistance, and impact resistance. It is useful as various industrial materials such as packaging materials. In particular, since the propylene-based resin composition of the present invention has a high MFR and rich fluidity, it can be suitably used for each application in injection molding.

(5) Molded product The molded product of the present invention is a molded product obtained by injection molding the propylene-based resin composition of the present invention. The molded product obtained by this is not limited by its shape and size, and examples thereof include a plate-like body, a container or a container lid.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In addition, the physical-property measurement, analysis, etc. in a following example follow the following method.

(1) Melt flow rate (MFR)
According to JIS K7210A method and condition M, measurement was performed under the following conditions. The unit is g / 10 minutes.
Test temperature: 230 ° C., nominal load: 2.16 kg, die shape: diameter 2.095 mm, length 8.000 mm.
(2) Melting temperature (Tm)
Measurements were made using a Seiko DSC. After taking 5.0 mg of sample and holding it at 200 ° C. for 5 minutes, it is crystallized at a rate of temperature decrease of 10 ° C./min to 40 ° C. to erase its thermal history, and further melted at a rate of temperature increase of 10 ° C./min. The peak temperature of the melting curve is taken as the melting point. When a plurality of melting points are observed in the resin, the one observed at the highest temperature is taken as the melting point of the resin.
(3) Ethylene content and weight average molecular weight It analyzed with the apparatus which combined the temperature rising solubility fractionation apparatus, GPC, and FT-IR. Details are described above.
(4) Melt Viscoelasticity Measurement (4-1) Measurement of G ′ and G ″ Obtained by performing frequency insertion experiment at 200 ° C. with a parallel 25 mm parallel plate using ARES manufactured by TA Instruments. .
(4-2) Extension viscosity measurement Device: ARES manufactured by TA Instruments
Geometry: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
Preparation of test piece: A sheet of 18 mm × 10 mm and a thickness of 0.7 mm is formed by press molding.
λmax calculation method:
The elongational viscosity at a strain rate of 0.1 / sec is plotted as a log-log graph of time t (seconds) on the horizontal axis and elongational viscosity ηE (Pa · seconds) on the vertical axis. On the logarithmic graph, the viscosity immediately before strain hardening is approximated by a straight line, the maximum value (ηmax) of the extensional viscosity ηE until the amount of strain reaches 4.0 is obtained, and on the approximate straight line up to that time Let ηlin be the viscosity. ηmax / ηlin is defined as λmax.
(5) Measurement of particle size of dispersed phase in component (A) The propylene-ethylene copolymer (A) was cut out perpendicularly to the extrusion direction from pellets obtained by granulation by the procedure described below. The section was used as a sample, which was stained with ruthenium tetroxide, and an observation image was obtained with a transmission electron microscope. The number average equivalent-circle particle diameter was determined by image analysis.
(6) Flexural properties Flexural elasticity: The flexural modulus of the composition was evaluated under the following conditions.
Standard number: Compliant with JIS K-7171 (ISO178) Testing machine: Precision universal testing machine Autograph AG-20kNG (manufactured by Shimadzu Corporation)
Specimen sampling direction: Flow direction Specimen shape: Thickness 4 mm, width 10 mm, length 80 mm
Test piece preparation method: Injection molding Condition adjustment: Leave in a temperature-controlled room adjusted to room temperature 23 ° C and humidity 50% for more than 24 hours Test room: Temperature-controlled room temperature adjusted to room temperature 23 ° C and humidity 50% Number of test pieces : 5
Distance between fulcrums: 32.0mm
Test speed: 1.0 mm / min
(7) Impact strength Impact resistance was evaluated by Charpy impact test.
Standard number: Compliant with JIS K7111 (ISO 179 / 1eA) Tester: Toyo Seiki Co., Ltd., fully automatic Charpy impact tester (with constant temperature bath)
Shape of test piece: Test piece with single notch (thickness 4 mm, width 10 mm, length 80 mm)
Notch shape: Type A notch (notch radius 0.25mm)
Impact speed: 2.9 m / s
Nominal pendulum energy: 4J
Test piece preparation method: Notch cut into injection molded test piece (ISO 2818 compliant)
Condition adjustment: 24 hours or more in a temperature-controlled room adjusted to room temperature 23 ° C./humidity 50% Test room: Temperature-controlled room temperature adjusted to room temperature 23 ° C./humidity 50%
Test temperature: 23 ° C
Evaluation item: Absorbed energy (8) Composition analysis:
A calibration curve was prepared by chemical analysis according to JIS method and measured by fluorescent X-ray.

[Synthesis example 1 of catalyst component (A)]:
(1) Synthesis of dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) indenyl}] hafnium: (component [A-1] Synthesis):
(1-a) Synthesis of 4- (4-t-butylphenyl) -indene:
1-Bromo-4-t-butyl-benzene (40 g, 0.19 mol) and dimethoxyethane (400 ml) were added to a 1000 ml glass reaction vessel, and cooled to -70 ° C. A t-butyllithium-pentane solution (260 ml, 0.38 mol, 1.46 mol / L) was added dropwise thereto. After dropping, the mixture was stirred for 5 hours while gradually returning to room temperature. The mixture was cooled again to −70 ° C., and a dimethoxyethane solution (100 ml) of triisopropyl borate (46 ml, 0.20 mol) was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.

Distilled water (100 ml) was added to the reaction solution, and the mixture was stirred for 30 minutes, and then sodium carbonate 50 g in water (150 ml), 4-bromoindene (30 g, 0.15 mol), tetrakis (triphenylphosphino) palladium (5 g, 4 g .3 mmol) was added in turn, after which the low boiling components were removed and heated at 80 ° C. for 5 hours.
The reaction solution was poured into ice water (1 L), from which ether was extracted three times, and the ether layer was washed with saturated brine until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 4- (4-tert-butylphenyl) -indene (37 g, yield 98%) as a pale yellow liquid.

(1-b) Synthesis of 2-bromo-4- (4-t-butylphenyl) -indene:
To a 1000 ml glass reaction vessel, 4- (4-t-butylphenyl) -indene (37 g, 0.15 mol), dimethyl sulfoxide (400 ml) and distilled water (11 ml) were added, and N-bromosuccinimide (35 g) was added thereto. , 0.20 mol) was gradually added, and the mixture was stirred at room temperature for 1 hour.
The reaction solution was poured into ice water (1 L), and extracted from it three times with toluene. The toluene layer was washed with saturated brine, p-toluenesulfonic acid (4.3 g, 22 mmol) was added, and the mixture was heated to reflux for 2 hours while removing moisture.
The reaction solution was transferred to a separatory funnel and washed with brine until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to give 2-bromo-4- (4-t-butylphenyl) -indene (46 g, yield 95%) as a pale yellow solid. Obtained.

Synthesis of (1-c) 4- (4-t-butylphenyl) -2- (5-methyl-2-furyl) -indene:
Methyl furan (13.8 g, 0.17 mol) and dimethoxyethane (400 ml) were added to a 1000 ml glass reaction vessel and cooled to -70 ° C. An n-butyllithium-hexane solution (111 ml, 0.17 mol, 1.52 mol / L) was added dropwise thereto. After dropping, the mixture was stirred for 3 hours while gradually returning to room temperature. The mixture was cooled again to 70 ° C., and a dimethoxyethane solution (100 ml) containing triisopropyl borate (41 ml, 0.18 mol) was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
Distilled water (50 ml) was added to the reaction solution, and the mixture was stirred for 30 minutes, and then an aqueous solution (100 ml) of sodium carbonate 54 g, 2-bromo-4- (4-t-butylphenyl) -indene (46 g, 0.14 mol), Tetrakis (triphenylphosphino) palladium (5 g, 4.3 mmol) was added in order, and then heated while removing low boiling components and heated at 80 ° C. for 3 hours.
The reaction solution was poured into ice water (1 L), from which ether was extracted three times, and the ether layer was washed with saturated brine until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, the residue was purified with a silica gel column, recrystallized with hexane, and 4- (4-t-butylphenyl) -2- (5-methyl-2-furyl)- Indene (30.7 g, 66% yield) was obtained as colorless crystals.

Synthesis of (1-d) dimethylbis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} silane:
4- (4-t-Butylphenyl) -2- (5-methyl-2-furyl) -indene (22 g, 66 mmol) and THF (200 ml) are added to a 1000 ml glass reaction vessel and cooled to -70 ° C. did. An n-butyllithium-hexane solution (42 ml, 67 mmol, 1.60 mol / L) was added dropwise thereto. After dropping, the mixture was stirred for 3 hours while gradually returning to room temperature. The mixture was cooled again to −70 ° C., 1-methylimidazole (0.3 ml, 3.8 mmol) was added, and a THF solution (100 ml) containing dimethyldichlorosilane (4.3 g, 33 mmol) was added dropwise. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, transferred to a separatory funnel, and washed with brine until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column. Dimethylbis (2- (5-methyl-2-furyl) -4- (4-t-butylphenyl))-indenyl) A pale yellow solid of silane (22 g, 92% yield) was obtained.

Synthesis of (1-e) rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium:
In a 500 ml glass reaction vessel, 9.6 g (13.0 mmol) of dimethylbis (2- (5-methyl-2-furyl) -4- (4-tert-butylphenyl) -indenyl) silane, 300 ml of diethyl ether. And cooled to -70 ° C in a dry ice-methanol bath. 16 ml (26 mmol) of a 1.59 mol / liter n-butyllithium-hexane solution was added dropwise thereto. After dropping, the mixture was returned to room temperature and stirred for 3 hours. The solvent of the reaction solution was distilled off under reduced pressure, 250 ml of toluene and 10 ml of diethyl ether were added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added 4.2 g (13.0 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure, recrystallization was performed with dichloromethane / hexane, and dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl)- Indenyl}] 1.3 g of hafnium racemate (purity 99% or more) was obtained as yellow-orange crystals (yield 22%).

The resulting proton nuclear magnetic resonance method for racemate identified value according to ^{(1 H-NMR)} are shown below.
_{^{[1 H-NMR (CDCl 3}} ) identification results:
Racemate: δ 0.95 (s, 6H), δ 1.18 (s, 18H), δ 2.09 (s, 6H), δ 5.80 (d, 2H), δ 6.37 (d, 2H), δ6. 75 (dd, 2H), δ 7.09 (d, 2H), δ 7.34 (s, 2H), δ 7.33 (d, 2H), δ 7.35 (d, 4H), δ 7.87 (d, 4H ).

[Synthesis Example 2 of Catalyst Component (A)]:
(1) Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium: (synthesis of component [A-2] ):
The synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium is described in Example 1 of JP 2000-95791 A. Was carried out in the same manner as described in.

[Catalyst Synthesis Example 1]
(1-1) Chemical treatment of ion-exchange layered silicate:
In a separable flask, 96% sulfuric acid (1044 g) was added to 3456 g of distilled water, and then 600 g of montmorillonite (Mizusawa Chemical Benclay SL: average particle size 19 μm) was added as a layered silicate. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, added with 2400 g of distilled water and then filtered to obtain 1230 g of a cake-like solid.
Next, 648 g of lithium sulfate and 1800 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution, and the entire amount of the above solid on the cake was added, and 522 g of distilled water was further added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, filtered after adding 1980 g of distilled water, further washed with distilled water to pH 3, and filtered to obtain 1150 g of cake-like solid.
The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed, and further, rotary kiln drying was performed under a condition of 215 ° C. under a nitrogen stream for a residence time of 10 minutes. 340 g was obtained.
The composition of this chemically treated smectite is Al: 7.81 wt%, Si: 36.63 wt%, Mg: 1.27 wt%, Fe: 1.82 wt%, Li: 0.20 wt%, Al / Si = 0.222 [mol / mol].

(1-2) Catalyst preparation and prepolymerization:
Into a three-necked flask (volume: 1 L), 10 g of the chemically treated smectite obtained above was added, and heptane (65 mL) was added to form a slurry, to which was added a triisobutylaluminum (25 mmol: heptane solution having a concentration of 143 mg / mL). 6 mL) and stirred for 1 hour, washed to 1/100 with heptane, and heptane was added to a total volume of 100 mL.
In another flask (volume: 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl)-] prepared in Synthesis Example 1 of the catalyst component (A) was used. 4- (4-t-butylphenyl) indenyl}] hafnium (105 μmol) is dissolved in toluene (30 mL) (solution 1), and further, the catalyst component (A) is synthesized in another flask (volume 200 mL). Rac-dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium (45 μmol) prepared in Example 2 was dissolved in toluene (12 mL). (Solution 2).

After adding triisobutylaluminum (0.6 mmol: 0.83 mL of a heptane solution with a concentration of 143 mg / mL) to the 1 L flask containing the chemically treated smectite, add the above solution 1, and then add the above solution 2 after 5 minutes. And stirred at room temperature for 1 hour.
Thereafter, 356 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was performed while maintaining 40 ° C. for 2 hours. Thereafter, the propylene feed was stopped, the temperature was raised to 50 ° C., and residual polymerization was performed until the pressure in the autoclave reached 0.05 MPa. After removing the supernatant of the resulting catalyst slurry by decantation, triisobutylaluminum (6 mmol: 8.3 mL of a heptane solution having a concentration of 143 mg / mL) was added to the remaining portion and stirred for 5 minutes.
This solid was dried under reduced pressure for 2 hours to obtain 28.4 g of a dry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.84 (preliminary polymerization catalyst 1).

[Catalyst synthesis example 2]
(1-1) Chemical treatment of ion-exchange layered silicate Into a 3 L separable flask equipped with a stirring blade and a reflux device, 2250 g of pure water was added, 665 g of 98% sulfuric acid was added dropwise, and the internal temperature was adjusted to 90 ° C. . Further, 400 g of commercially available granulated montmorillonite (Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 47.1 μm) was added and stirred. Then, it was made to react at 90 degreeC for 3 hours. This slurry was filtered with a Nutsche and a suction bottle connected to an aspirator, and washed 5 times with 2 L of pure water.
The cake recovered in this manner was added to an aqueous solution in which 423 g of zinc sulfate heptahydrate was dissolved in 1523 ml of pure water in a 5 L beaker and reacted at room temperature for 2 hours. This slurry was filtered through a device in which an aspirator was connected to Nutsche and a suction bottle, washed 5 times with 2 L of pure water to recover a cake, and dried at 120 ° C. overnight to obtain 296 g of chemically treated montmorillonite. . This was sieved with a sieve having an opening of 74 μm to remove the content on the sieve.
The chemically treated montmorillonite obtained above was put into a 1 L flask and dried under reduced pressure at 200 ° C. for 3 hours. Thereafter, it was further dried under reduced pressure for 2 hours to obtain a treated montmorillonite.
(1-2) Catalyst preparation and prepolymerization:
Into a three-necked flask (volume: 1 L), 10 g of the chemically treated smectite obtained above was added, and heptane (66 mL) was added to form a slurry. To this, 34 mL of triisobutylaluminum (25 mmol: 140 mg / mL heptane solution) was added. ) And stirred for 1 hour, washed to 1/100 with heptane, and heptane was added so that the total volume became 100 mL.
In another flask (volume: 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4) prepared in Synthesis Example 2 of the catalyst component (A) was prepared. -Biphenylyl) -4-hydroazurenyl}] hafnium (0.30 mmol) was dissolved in heptane (60 mL).
Triisobutylaluminum (1.2 mmol: 1.67 mL of a heptane solution having a concentration of 143 mg / mL) was added to the 1 L flask containing the chemically treated smectite, and the complex solution was further added, followed by stirring at room temperature for 60 minutes. . Thereafter, 340 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was performed while maintaining 40 ° C. for 4 hours. Thereafter, propylene feed was stopped, and residual polymerization was performed for 2.0 hours. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (12 mmol: 17 mL of a heptane solution having a concentration of 140 mg / mL) was added and stirred for 10 minutes. This solid was dried under reduced pressure for 2 hours to obtain 25.5 g of a dry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.55. (Preliminary polymerization catalyst 2)

[Production Example 1]
First step polymerization:
The 3 L autoclave was dried well by circulating nitrogen under heating, and then the inside of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL), 200 Nml of hydrogen was introduced, 750 g of liquid propylene was introduced, and the temperature was raised to 75 ° C.
Thereafter, 65 mg of the prepolymerized catalyst 1 synthesized in Catalyst Synthesis Example 1 in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 75 ° C. for 30 minutes, unreacted propylene was quickly purged, and the inside of the autoclave was purged with nitrogen to stop the polymerization in the first step.
Using a Teflon (registered trademark) tube from the nitrogen-substituted autoclave, 24 g of the polymer after the first step was collected and analyzed.

Second step polymerization:
After maintaining the above nitrogen-substituted autoclave at 70 ° C. and atmospheric pressure, propylene was added at a partial pressure of 0.5 MPa, and ethylene was then added at a partial pressure of 1.5 MPa to start polymerization in the second step. During the polymerization, a mixed gas of ethylene / propylene, which had been adjusted in advance so as to have a constant composition, was introduced and maintained at a total pressure of 2.0 MPa and maintained at 70 ° C.
The average gas composition of the polymerization in the second step was C2: 78.0%.
After 380 minutes, the polymerization was stopped by purging an unreacted ethylene / propylene mixed gas. As a result, 318 g of a polymer was obtained.
The analysis results of the propylene-ethylene copolymer (A) thus obtained are shown in Table 1. Further, when the melt viscoelasticity measurement of the propylene-ethylene copolymer (A) was performed, G ′> G ″ was obtained at an angular frequency of 0.01 rad / s, and λmax was 1.1.

[Production Example 2]
First step polymerization:
The 3 L autoclave was dried well by circulating nitrogen under heating, and then the inside of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL), 200 Nml of hydrogen was introduced, 750 g of liquid propylene was introduced, and the temperature was raised to 75 ° C.
Thereafter, 65 mg of the prepolymerized catalyst 1 synthesized in Catalyst Synthesis Example 1 in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 75 ° C. for 45 minutes, unreacted propylene was quickly purged and the inside of the autoclave was purged with nitrogen to stop the polymerization in the first step.
Using a Teflon (registered trademark) tube from the nitrogen-substituted autoclave, 26 g of the polymer after the first step was collected and analyzed.

Second step polymerization:
After maintaining the above nitrogen-substituted autoclave at 60 ° C. and atmospheric pressure, propylene was added at a partial pressure of 0.5 MPa, and then ethylene was added at a partial pressure of 1.5 MPa to start polymerization in the second step. During the polymerization, a mixed gas of ethylene / propylene, which had been adjusted in advance so as to have a constant composition, was introduced to maintain the total pressure at 2.0 MPa and maintained at 60 ° C.
The average gas composition of the polymerization in the second step was C2: 78.0%.
After 350 minutes, polymerization was stopped by purging an unreacted ethylene / propylene mixed gas. As a result, 374 g of a polymer was obtained.
The analysis results of the propylene-ethylene copolymer (A) thus obtained are shown in Table 1. Further, when melt viscoelasticity measurement was performed, G ′> G ″ at an angular frequency of 0.01 rad / s, and λmax was 1.0.

[Production Example 3]
(I) Production of solid catalyst component (a) 20 liters of dehydrated and deoxygenated n-heptane was introduced into a tank equipped with a stirrer with an internal volume of 50 liters purged with nitrogen, and then 10 moles of magnesium chloride and 20 moles of tetrabutoxytitanium And then reacting at 95 ° C. for 2 hours, lowering the temperature to 40 ° C., introducing 12 liters of methylhydropolysiloxane (viscosity 20 centistokes) and further reacting for 3 hours, then taking out the reaction solution The resulting solid component was washed with n-heptane.
Subsequently, 5 liters of dehydrated and deoxygenated n-heptane was introduced into the tank using the tank equipped with a stirrer, and then 3 mol of the solid component synthesized above was introduced in terms of magnesium atom. Next, 5 liters of silicon tetrachloride was mixed with 2.5 liters of n-heptane and introduced at 30 ° C. for 30 minutes. The temperature was raised to 70 ° C. and reacted for 3 hours. Then, the reaction solution was taken out, The resulting solid component was washed with n-heptane.
Subsequently, 2.5 liters of dehydrated and deoxygenated n-heptane was introduced into the tank using the tank with a stirrer, and 0.3 mol of phthalic acid chloride was mixed and introduced at 90 ° C. for 30 minutes. And reacted at 95 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Next, 2 liters of titanium tetrachloride was added at room temperature, and the temperature was raised to 100 ° C., followed by reaction for 2 hours. After completion of the reaction, washing with n-heptane was performed. Further, 0.6 liters of silicon tetrachloride and 8 liters of n-heptane were introduced, reacted at 90 ° C. for 1 hour, and sufficiently washed with n-heptane to obtain a solid component. This solid component contained 1.30% by weight of titanium.
Next, 8 liters of n-heptane, 400 g of the solid component obtained above, 0.27 mol of t-butyl-methyl-dimethoxysilane and 0.27 mol of vinyltrimethylsilane were introduced into the tank equipped with a stirrer substituted with nitrogen. And contacted at 30 ° C. for 1 hour. Next, the mixture was cooled to 15 ° C., 1.5 mol of triethylaluminum diluted in n-heptane was introduced over 15 minutes under 15 ° C., and after the introduction, the temperature was raised to 30 ° C. and reacted for 2 hours. -Washing with heptane gave 390 g of solid catalyst component (a).
The obtained solid catalyst component (a) contained 1.22% by weight of titanium.
Further, 6 liters of n-heptane and 1 mol of triisobutylaluminum diluted in n-heptane were introduced over 30 minutes under 15 ° C., and then about 0.4 kg of propylene was controlled so as not to exceed 20 ° C. Per hour for 1 hour and prepolymerized.
As a result, a polypropylene-containing solid catalyst component (a) in which 0.9 g of propylene was polymerized per 1 g of solid was obtained.

(Ii) Production of propylene-based block copolymer [Pre-stage polymerization step: Production of crystalline propylene polymer component]
Polymerization was carried out using a continuous reaction apparatus in which two fluidized bed reactors having an internal volume of 230 liters were connected.
First, in a first reactor, a polymerization temperature of 75 ° C., a propylene partial pressure of 18 kg / cm ² (absolute pressure), and hydrogen as a molecular weight control agent are continuously added so that the molar ratio of hydrogen / propylene is 0.040. While feeding, triethylaluminum was fed at 5.25 g / hr as a solid catalyst component (a) so that the polymer polymerization rate was 20 kg / hr to produce a crystalline propylene polymer component.
The powder polymerized in the first reactor (crystalline propylene polymer component) was continuously withdrawn so that the amount of powder held in the reactor was 60 kg, and continuously transferred to the second reactor.

[Second-stage polymerization step: Production of propylene / ethylene random copolymer component]
Subsequently, propylene and ethylene were continuously fed so that the molar ratio of ethylene / propylene was 0.40 so that the inside of the second reactor had a polymerization temperature of 80 ° C. and a pressure of 2.0 MPa, Hydrogen as a molecular weight control agent is continuously supplied so that the molar ratio of hydrogen / (propylene + ethylene) is 0.0070, and ethyl alcohol as an active hydrogen compound is 1.5 times that of triethylaluminum. The propylene / ethylene random copolymer component was produced by supplying the solution so as to have a molar ratio.
The powder that has been polymerized in the second reactor (a propylene-based block copolymer comprising a crystalline propylene polymer component and a propylene / ethylene random copolymer component) has a powder holding amount of 40 kg in the reactor. And continuously extracted into a vessel. Nitrogen gas containing water was supplied to stop the reaction to obtain a propylene-based block copolymer.
The analysis results of the propylene-ethylene copolymer (B) thus obtained are shown in Table 1. Further, when melt viscoelasticity measurement was performed, G ′ <G ”was obtained at an angular frequency of 0.01 rad / s, and λmax was 1.0.

[Production Example 4]
Using the catalyst and polymerization method used in Production Example 3, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.060, the hydrogen / (propylene + ethylene) molar ratio in the latter polymerization step was 0.0135, ethyl alcohol A propylene-based block copolymer was produced in the same manner as in Production Example 3 except that the amount was changed so as to be 1.4 times mol with respect to triethylaluminum.
The analysis results of the propylene-ethylene copolymer (B) thus obtained are shown in Table 1. Further, when melt viscoelasticity measurement was performed, G ′ <G ”was obtained at an angular frequency of 0.01 rad / s, and λmax was 1.0.

[Production Example 5]
First step polymerization:
The 3 L autoclave was dried well by circulating nitrogen under heating, and then the inside of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL), 500 Nml of hydrogen was introduced, 750 g of liquid propylene was introduced, and the temperature was raised to 75 ° C.
Thereafter, 40 mg of the prepolymerized catalyst 2 synthesized in Catalyst Synthesis Example 2 in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 75 ° C. for 60 minutes, unreacted propylene was quickly purged, and the inside of the autoclave was purged with nitrogen to stop the polymerization in the first step.
Using a Teflon (registered trademark) tube from the nitrogen-substituted autoclave, 23 g of the polymer after the first step was collected and analyzed.

Second step polymerization:
After maintaining the above nitrogen-substituted autoclave at 70 ° C. and atmospheric pressure, propylene was added at a partial pressure of 0.5 MPa, and ethylene was then added at a partial pressure of 1.5 MPa to start polymerization in the second step. During the polymerization, a mixed gas of ethylene / propylene, which had been adjusted in advance so as to have a constant composition, was introduced and maintained at a total pressure of 2.0 MPa and maintained at 70 ° C.
The average gas composition of the polymerization in the second step was C2: 80.0%.
After 215 minutes, polymerization was stopped by purging an unreacted ethylene / propylene mixed gas. As a result, 316 g of a polymer was obtained.
The analysis results of the propylene-ethylene copolymer (B) thus obtained are shown in Table 1. Further, when melt viscoelasticity measurement was performed, G ′ <G ”was obtained at an angular frequency of 0.01 rad / s, and λmax was 1.0.

[Examples 1-5, Comparative Examples 1-3]
Examples 1-5 mix the propylene-ethylene copolymer (A) and propylene-ethylene copolymer (B) obtained by the said manufacture example by the mixing | blending of Table 3, and granulate on the following conditions. The physical properties of the molded product were evaluated. In Comparative Examples 1 to 3, only the propylene-ethylene copolymer (B) was used. The granulation conditions and molding conditions are shown below. The physical property evaluation results are shown in Table 3.

(With additives):
Antioxidant: Tetrakis {methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate} methane 500 ppm, Tris (2,4-di-t-butylphenyl) phosphite 500 ppm Neutralizing agent: calcium stearate 500 ppm.
(Granulation):
Extruder: KZW-15-45MG twin screw extruder manufactured by Technobel Co., Ltd. Screw: 15 mm in diameter, L / D = 45
Extruder set temperature: (from below the hopper) 40, 80, 160, 200, 200, 200 (die temperature)
Screw rotation speed: 400rpm
Discharge amount: Adjusted to about 1.5 kg / hr with a screw feeder Die: 3 mm diameter, strand die, 2 holes (molded):
The obtained raw material pellets were injection molded under the following conditions to obtain flat plate test pieces for evaluating physical properties.
Standard number: JIS K7152 (ISO 294-1)
Reference molding machine: EC20P injection molding machine manufactured by Toshiba Machine Co., Ltd. Molding machine set temperature: 80, 210, 210, 200, 200 ° C (from the bottom of the hopper)
Mold temperature: 40 ℃
Injection speed: 52 mm / s (screw speed)
Holding pressure: 30 MPa
Holding pressure time: 8 seconds Mold shape: 2 flat plates (thickness 4 mm, width 10 mm, length 80 mm)

[Example 6, Comparative Example 4]
The procedure was the same as Example 1 or Comparative Example 1 except that the resin composition was changed as shown in Table 4. The physical property evaluation results are shown in Table 4. The elastomers and talc used are as follows.
Elastomer: Ethylene-butene rubber (Tafmer A1050S manufactured by Mitsui Chemicals, Inc .: MFR at 230 ° C. under a load of 2.16 kg = 2.4 g / 10 min.)
Talc (PKP53 manufactured by Fuji Talc: average particle size 5.9 μm, aspect ratio 6)

"Consideration by comparison of Example and Comparative Example"
When Examples 1 to 3 and Comparative Example 1, Example 4 and Comparative Example 2, and Example 5 and Comparative Example 3 are respectively compared, those containing the copolymer component (A) balance between rigidity and impact resistance. However, it is clear that this is improved as compared with those not containing the copolymer component (A).
Further, when Example 6 and Comparative Example 4 are compared, the composition containing the elastomer component and the talc component also includes the copolymer component (A), and the balance between rigidity and impact resistance is the copolymer component. It is clear that this is an improvement over those not containing (A).

Claims (5)

0.1 to 30% by weight of propylene-ethylene copolymer component (A) and 70 to 99.9% by weight of propylene-ethylene copolymer component (B),
The propylene-ethylene copolymer component (A) is obtained by continuously multistage polymerization of a crystalline propylene polymer component and a propylene-ethylene random copolymer component, and has the following characteristics (A1) to (A6): Have
The propylene-ethylene copolymer component (B) is obtained by continuously multistage polymerization of a crystalline propylene polymer component and a propylene-ethylene random copolymer component, and has the following characteristics (B1) to (B3): Propylene-based resin composition characterized by having.
(A1) The amount of the component (AC) mainly composed of crystalline polypropylene, which is fractionated and determined by the temperature-programmed crystalline fractionation method, is 10 to 98 weights with respect to the total amount of the propylene-ethylene copolymer (A). The amount of the component (AA) mainly consisting of a propylene-ethylene random copolymer is 2 to 90% by weight,
(A2) The melt flow rate (MFRA) at 230 ° C. and a load of 2.16 kg of the propylene-ethylene copolymer (A) is 10 g / 10 min. That's it,
(A3) The melting point in DSC of the propylene-ethylene copolymer (A) is 156.1 ° C. or higher,
(A4) The melt flow rate MFRA-1 of the crystalline polypropylene component polymerized in the first stage is 40 g / 10 min. That's it,
(A5) The ethylene content of the copolymer component (AA) fractionated by the temperature rising crystalline fractionation method is based on the total amount of propylene and ethylene monomer in the copolymer component (AA). 20 to 80% by weight,
(A6) The melt flow rate MFRA-2 of the copolymer component (A) polymerized in the second stage is obtained by the following formula 1 ′, and the weight average molecular weight M _w AA of the component (AA) The following formula 1 is satisfied.
log (MFRA-2) ≦ −3.9 × log (MwA−A) +19.9 (Equation 1)
log (MFRA) = {weight% of component (AC)} / 100 × log (MFRA-1) + {weight% of component (AA)} / 100 × log (MFRA-2) ( Formula 1 ')
(B1) The amount of the component (BC) mainly composed of crystalline polypropylene, which is fractionated and quantified by the temperature rising crystalline fractionation method, is 50 to 95 weights with respect to the total amount of the propylene-ethylene copolymer (B). The amount of the component (BA) mainly composed of a propylene-ethylene random copolymer is 5 to 50% by weight,
(B2) The melting point in DSC of the propylene-ethylene copolymer (B) is 155 ° C. or higher,
(B3) The melt flow rate MFRB-2 in the second stage in polymerized copolymer component (B), determined by the following formula 2 ', and the weight average molecular weight of the component _{(B-A) M w B} -A The following formula 2 is satisfied.
log (MFRB-2)> − 3.9 × log (MwB−A) +21.4 (Expression 2)
log (MFRB) = {weight% of component (BC)} / 100 × log (MFRB-1) + {weight% of component (BA)} / 100 × log (MFRB-2) (...) Formula 2 ′)
Here, MFRB is the MFR of the entire propylene-ethylene copolymer (B).   2. The propylene-based resin composition according to claim 1, wherein a parameter λmax indicating strain hardening obtained from an extensional viscosity measurement of the propylene-ethylene copolymer (A) is less than 2.0. 3. The propylene-based resin composition according to claim 1, wherein the propylene-ethylene copolymer (A) contains, as a part thereof, a graft copolymer having a crystalline polypropylene component as a branch part. 4. The propylene-based resin composition according to any one of claims 1 to 3 , comprising 0 to 40% by weight of an ethylene / α-olefin-based elastomer or styrene-based elastomer and 0 to 40% by weight of an inorganic filler. A propylene-based resin composition. Claim 1 molded article obtained by injection molding the propylene resin composition according to any one of 4.